Multi-chromophoric azo pyridone colorants

ABSTRACT

Disclosed is a compound comprising three or more moieties of the formula  
                 
 
said moieties being bonded to a central atom, monomeric group of atoms, oligomer, or polymer. Also disclosed is a phase change ink composition comprising a phase change ink carrier and a colorant compound comprising three or more moieties of the formula  
                 
said moieties being bonded to a central atom, monomeric group of atoms, oligomer, or polymer.

BACKGROUND

Disclosed herein are colorant compounds. More specifically, disclosedherein are colorant compounds particularly suitable for use in hot meltor phase change inks. One embodiment is directed to a compoundcomprising three or more moieties of the formula

wherein (A) each R₁, independently of the others, is (i) an alkyl oralkylene group, (ii) an aryl or arylene group, (iii) an arylalkyl orarylalkylene group, (iv) an alkylaryl or alkylarylene group, (v) a silylor silylene group, or (vi) a siloxy group, (B) each R₂, independently ofthe others, is (i) an alkyl or alkylene group, (ii) an aryl or arylenegroup, (iii) an arylalkyl or arylalkylene group, (iv) an alkylaryl oralkylarylene group, (v) a silyl or silylene group, (vi) a siloxy group,or (vii) a group of the formula

wherein r and s are each, independently of the other, integersrepresenting a number of repeat —CH₂— groups, (C) each R₃, independentlyof the others, is (i) an alkyl group, (ii) an aryl group, (iii) anarylalkyl group, or (iv) an alkylaryl group, (D) each X, independentlyof the others, is (i) a direct bond, (ii) an oxygen atom, (iii) a sulfuratom, (iv) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and (E) each Z,independently of the others, is (i) a hydrogen atom, (ii) a halogenatom, (iii) a nitro group, (iv) an alkyl group, (v) an aryl group, (vi)an arylalkyl group, (vii) an alkylaryl group, (viii) a group of theformula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, a silyl group, or a siloxy group, (ix) a sulfonyl groupof the formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group,an aryl group, an arylalkyl group, an alkylaryl group, a silyl group, ora siloxy group, or (x) a phosphoryl group of the formula —PO₃R₉₀ whereinR₉₀ is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, a silyl group, or a siloxy group; saidmoieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer. Another embodiment is directed to a phase changeink comprising a phase change ink carrier and a colorant compoundcomprising three or more moieties of the formula

said moieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 6,576,747 (Carlini et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forpreparing dianthranilate compounds which comprises (a) admixingreactants as follows: (1) a diol of the formula R₁(OH)₂, wherein R₁ isan alkylene group having at least about 20 carbon atoms, and wherein the—OH groups are primary or secondary, (2) isatoic anhydride, present inan amount of at least about 2 moles of isatoic anhydride per every onemole of diol, (3) a catalyst which is 1,4-diazabicyclo(2.2.2)octane,N,N,N′,N′-tetramethylethylene diamine, or a mixture thereof, saidcatalyst being present in an amount of at least about 0.2 mole ofcatalyst per every one mole of diol, and (4) a solvent; and (b) heatingthe mixture thus formed to form a dianthranilate compound of the formula

Also disclosed is a process for preparing diazopyridone colorants whichcomprises (I) preparing a dianthranilate compound by the aforementionedmethod, (II) reacting the dianthranilate compound with nitrosylsulfuricacid to form a diazonium salt, and (III) reacting the diazonium saltwith a pyridone compound to form a diazopyridone compound.

U.S. Pat. No. 6,713,614 (Carlini et al.), the disclosure of which istotally incorporated herein by reference, discloses compounds of theformula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,663,703 (Wu et al.), the disclosure of which is totallyincorporated herein by reference, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

U.S. Pat. No. 6,755,902 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

U.S. Pat. No. 6,590,082 (Banning et al.), the disclosure of which istotally incorporated herein by reference, discloses compounds of theformula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,696,552 (Mayo et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forpreparing substituted pyridone compounds which comprises (a) admixing inthe absence of a solvent (1) an amine of the formula R₁—NH₂ wherein R₁is an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, and (2) a first ester of the formula

wherein R₂ is an electron withdrawing group and R₃ is an alkyl group;(b) heating the mixture containing the amine and the first ester to forman intermediate compound of the formula

(c) admixing the intermediate compound with (1) a base and (2) a secondester of the formula

wherein R₄ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group and R₅ is an alkyl group, said second ester beingpresent in a molar excess relative to the intermediate compound, saidbase being present in a molar excess relative to the intermediatecompound, and (d) heating the mixture containing the intermediatecompound, the second ester, and the base to form a pyridone compound ofthe formula

or a salt thereof. Also disclosed is a process for preparingdiazopyridone colorants which comprises preparing a pyridone compound bythe above process and reacting the pyridone compound with a diazoniumsalt to form a diazopyridone compound.

U.S. Pat. No. 6,576,748 (Carlini et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forpreparing a diazopyridone compound which comprises (a) preparing a firstsolution comprising (1) either (A) a dianiline of the formula

or (B) an aniline of the formula

and (2) a first solvent mixture comprising (I) a solvent, (II) aceticacid, and (III) an optional second acid, said acetic acid being presentin the solvent mixture in an amount of at least about 95 percent byweight of the solvent mixture, said first solution being at atemperature of about +15° C. or lower; (b) adding to the first solutionnitrosylsulfuric acid, thereby forming a diazonium salt either (A) ofthe formula

or (B) of the formula

(c) preparing a second solution comprising (1) a second solvent mixturecomprising water and an organic solvent soluble in or miscible in water,(2) either (A) a pyridone of the formula

or (B) a dipyridone of the formula

(3) a base present in an amount of at least about 3 molar equivalents ofbase per mole of pyridone moiety, and (4) an optional buffer salt, and(d) combining either (A) the second solution containing the dianilineand the first solution containing the pyridone, or (B) the secondsolution containing the aniline and the first solution containing thedipyridone to form a third solution and effect a coupling reaction toform a diazopyridone compound either (A) of the formula

or (B) of the formula

U.S. Pat. No. 6,646,111 (Carlini et al.), the disclosure of which istotally incorporated herein by reference, discloses compounds of theformula

The compounds are useful as colorants, particularly in applications suchas phase change inks.

U.S. Pat. No. 6,673,139 (Wu et al.), the disclosure of which is totallyincorporated herein by reference, discloses a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound of the formula

European Patent Publication 1 125 990 A1 and PCT Patent Publication WO01/09256 A1, the disclosures of each of which are totally incorporatedherein by reference, discloses an aqueous ink for ink jet recordingwhich contains at least a water-insoluble coloring matter, water, and aresin as main components and which takes the form of an emulsion, whichis characterized by containing at least one yellow hue coloring matterselected from the group consisting of a quinophthalone compoundrepresented by the formula (1)

wherein each of R₁ to R₃ independently represents a hydrogen atom, anunsubstituted or substituted alkyl group, —CONR₄R₅, or —COOR₆ (in whicheach of R₄ to R₆ independently represents a hydrogen atom, anunsubstituted or substituted alkyl group, or an unsubstituted orsubstituted aryl group) and all of R₁ to R₃ are not a hydrogen atom atthe same time, and a pyridone azo compound represented by the formula(2)

wherein each of R₇ to R₁₁ independently represents a hydrogen atom, ahalogen atom, an unsubstituted or substituted alkyl group, an aralkylgroup, an unsubstituted or substituted alkoxy group, an unsubstituted orsubstituted aryl group, an unsubstituted or substituted aryloxy group, ahydroxyl group, —NR₁₄R₁₅ (in which R₁₄ and R₁₅ independently represent ahydrogen atom, an unsubstituted or substituted alkyl group, or anaralkyl group), —COX₁ (in which X₁ represents an unsubstituted orsubstituted alkoxy group, an unsubstituted or substituted aryloxy group,or —NR₁₆R₁₇ (in which each of R₁₆ and R₁₇ independently represent ahydrogen atom, an unsubstituted or substituted alkyl group, an aralkylgroup, or an unsubstituted or substituted aryl group)),—COO(CH₂)_(n)—COX₂, —OCOX₃, or —NHCOX₄ (in which each of X₂ to X₄independently represents an unsubstituted or substituted alkyl group, anaralkyl group, an unsubstituted or substituted aryl group, anunsubstituted or substituted alkoxy group, or an unsubstituted orsubstituted aryloxy group, and n is an integer of 1 to 3), R₁₂represents an unsubstituted or substituted alkyl group, and R₁₃represents an unsubstituted or substituted alkyl group, an aralkylgroup, or an unsubstituted or substituted aryl group. The ink is for inkjet recording having excellent light resistance and storage stability,and enables formation of a high quality image without blotting, and theobtained recording image is excellent in water resistance.

PCT Patent Publication WO 01/21714, the disclosure of which is totallyincorporated herein by reference, discloses compositions comprising asolvent and at least one compound of the formula

in which R₁ represents H, an optionally substituted C₁₋₈ carbyl derivedgroup, or a group of the formula

where C is from 2 to 6, R³ represents optionally substituted C₁₋₈ carbylderived group, R⁴ and R⁵ independently represent an optionalsubstituent, R² represents an optionally substituted C₁₋₈ carbyl derivedgroup, X, Y, and Z independently represent H or an optional substituent,M represents H or a cation, and m and n independently represent 0, 1, or2. Also disclosed are compounds of the above formula providing that atleast one of R¹, R², X, Y, or Z comprises a group of formula SO₃M orPO₃M₂. These compositions and compounds are useful as the colorants toprepare color filters for displays.

U.S. Pat. No. 4,247,456 (von Brachel et al.), the disclosure of which istotally incorporated herein by reference, discloses water-insolublemonoazo dyes of the formula

wherein R is the residue of a benzene, naphthalene, diphenyl,diphenylmethane, or heterocyclic diazo compound which is free from watersolubilizing groups, produced by reacting a diazotized amine of thebenzene, naphthalene, diphenyl, diphenylmethane, or heterocyclic serieswhich is free from water solubilizing groups with the appropriate6-hydroxy-2-pyridone and the utility thereof for the dyeing and printingof synthetic fabric materials to yellow to red shades having excellentfastness to light and sublimation.

U.S. Pat. No. 3,957,749 (von Brachel et al.), the disclosure of which istotally incorporated herein by reference, discloses water-insolublemonoazo dyes of the formula

produced by reacting a diazotized amine of the benzene, naphthalene,diphenyl, diphenylmethane, or heterocyclic series which is free fromwater solubilizing groups with the appropriate 6-hydroxy-2-pyridone andthe utility thereof for the dyeing and printing of synthetic fabricmaterials to yellow to red shades having excellent fastness to light andsublimation.

Japanese Patent Publication JP 05331382, the disclosure of which istotally incorporated herein by reference, discloses a specific pyridoneazo pigment which is bright yellow and highly soluble in a solvent,absorbs light of long wavelength, and is useful for a thermal transfersheet. The pyridone azo pigment is represented by the formula

wherein R is H, alkyl, substituted alkyl, cycloalkyl, aryl, oroptionally substituted phenyl, and ring A is a benzene ring optionallyhaving a nonionic group. The pigment is prepared by diazotizing ananiline compound and coupling the resulting diazo compound with apyridone compound. Having a good solubility in an organic solvent and agood dispersibility in water, the pigment facilitates the preparation ofan ink containing a high concentration of the pigment homogeneouslydissolved or dispersed. The prepared ink enables the preparation of athermal transfer sheet coated with the ink uniformly in a high density.

British Patent 1,559,001 (Harvey et al.), the disclosure of which istotally incorporated herein by reference, discloses a hydrophilictextile material colored with a dyestuff of the formula

wherein D is the residue of a diazo or tetrazo component; R₁ is ahydrogen atom or an alkyl, chloro, acetamido, benzamido, carbamoyl, oran N-substituted carbamyl, for example —CONHBr, group or, preferably, acyano group; R₂ is an alkyl group, especially methyl, optionallysubstituted with a chlorine atom, a phenyl group, optionally substitutedwith an alkyl or alkoxy group, or a carboxylic acid or carboxylic acidester group; or R₁ and R₂ together with the carbon atoms in the 3- or4-position of the pyridone ring may form an alicyclic or aromatic ringsystem so that, for example, R₁ and R₂ together may be a tri- ortetra-methylene group forming with the pyridone of penteno (c) or hexeno(c) pyrid-2-one, or R₁ and R₂ may form together with the adjacent carbonatoms of the pyridone ring a benzene ring giving a benz (c) pyrid-2-one;R₃ is an aryl group carrying one or more substituents selected from —NO,—SO₂R¹, —COR¹, —COOR₁, —CF, or —CN, wherein R¹ is an optionallysubstituted alkyl or aryl group; and n is an integer which may be 1 or2.

German Patent Publication DE 19646430, the disclosure of which istotally incorporated herein by reference, discloses dye mixturescomprising at least two structurally different dyes, each correspondingto formula

wherein R₁ is C₁-C₄ alkyl; R₂ is the (CH₂)_(n)O—R₅ radical; R₅ is,independently of R₁, C₁-C₄ alkyl or phenyl (which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxy, or halogen); and n is2 or 3, which dye mixtures are suitable for dyeing or printing textilefibre materials (e.g. polyester materials), giving dyeings having goodaround fastness properties.

German Patent Publication DE 19646429, the disclosure of which istotally incorporated herein by reference, discloses dye mixturescomprising at least two structurally different dyes, each of which hasthe formula

in which R₁ is C₁-C₄ alkyl and R₂ is isopropyl, n-butyl, isobutyl,sec-butyl, or tert-butyl; or C₁-C₃ alkyl which is substituted by phenylor phenoxy; or R₁ is phenyl (which is unsubstituted or substituted byC₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxyl, or halogen), C₁-C₄ alkoxy-C₁-C₃alkylene, phenoxy-C₁-C₃ alkylene, or C₁-C₃ alkyl which is substituted byphenyl (which is unsubstituted or substituted by C₁-C₄ alkyl, C₁-C₄alkoxy, hydroxyl, or halogen) and R₂ is C₁-C₁₀ alkyl (which isunsubstituted or substituted by hydroxyl, OCOR₃, or phenoxy, where thephenyl ring in phenoxy is unsubstituted or substituted by C₁-C₄ alkyl,C₁-C₄ alkoxy, hydroxyl, or halogen) and the alkyl chain in C₁-C₁₀ alkylfrom C₂ can be interrupted by one or more oxygen atoms; phenyl (which isunsubstituted or substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxyl, orhalogen); or C₅-C₇ cycloalkyl; and R₃ is C₁-C₄ alkyl, are suitable fordyeing or printing textile fibre materials (e.g. polyester materials)and give dyeings with good allround properties.

German Patent Publication DE 19647869, the disclosure of which istotally incorporated herein by reference, discloses a dye mixturecontaining at least 2 dyes with different structures, each of formula

where R₁ is a 1-4C alkyl; and R₂ is a linear 1-3C alkyl. Also claimed ishydrophobic fibre material, preferably polyester textile material, dyedor printed with the mixture.

PCT Patent Publication WO 99/43754, the disclosure of which is totallyincorporated herein by reference, discloses compounds of the formula

and salts and tautomers thereof, wherein: R₁ and R₂ each independentlyis H, optionally substituted alkyl, optionally substituted aryl, oroptionally substituted arylalkyl; each W and each X independently is—COOH, —SO₃H, —PO₃H₂, or alkyl substituted by one or more groupsselected from —COOH, —SO₃H, and —PO₃H₂; each Y and each Z independentlyis a substituent other than those defined for W and X; a and d eachindependently is 1 to 5; b and c each independently is 0 to 4; (a+b) hasa value of 5 or less; and (c+d) has a value of 5 or less. Also claimedare inks containing a compound of this formula, an ink jet printingprocess using the inks, substrates printed with the inks, and ink jetprinter cartridges containing the inks.

U.S. Pat. No. 5,929,218 (Lee et al.), the disclosure of which is totallyincorporated herein by reference, discloses pyridone-based yellowmonoazo dyes used in thermal transfer having following formula whichhave good stability and hue

wherein R₁ is hydrogen atom; unsubstituted or substituted alkyl group offrom 1 to 8 carbon atoms with alkoxy or aryl; or unsubstituted orsubstituted aryl group with alkoxy or halogen, and X is hydrogen atom;alkyl group of from 1 to 4 carbon atoms; alkoxy group; or halogen; R₂ isselected from the following groups;

wherein R₃ and R₄ are independently selected from groups consistinghydrogen, substituted or unsubstituted alkyl group of from 1 to 4 carbonatoms, halogen, alkyl carboxylate, and carbonyl group; R₃-R₄ isnoncyclization with R₃ and R₄ and selected respectively from the abovesubstituents (R₃ and R₄); or saturated or unsaturated cycloalkyl of from3 to 6 carbon atoms, Z is nitro, halogen, alkyl group of from 1 to 4carbon atoms, alkoxy, sulfonyl, carbonyl, carboxyamide, sulfonamino,cyano, hydroxy, or hydrogen atom.

European Patent Publication EP 0 706 679 B1, U.S. Pat. No. 5,853,929(Campbell), and PCT Patent Publication WO 95/00885, the disclosures ofeach of which are totally incorporated herein by reference, disclosecolored cyan toner for electroreprography and laser printing based onSolvent Blue 70, and a trichomatic set of coloured toners based onSolvent Blue 70, benzodifuranone red dyes, and azo pyridone yellow dyesof the formula

wherein X is halogen, nitro, or a group —COOR⁵, R⁹ is C₁₋₄ alkyl, R¹⁰ isC₁₋₁₂ alkyl, R⁵ is C₁₋₈ alkyl or a group of formula—(C₁₋₃-alkylene)-(CO)_(q)-Z wherein q is 0 or 1 and Z is —OR⁶ or —NR⁶R⁷when q=1 or Z is —OR⁸ when q=0, R⁶ is selected from optionallysubstituted C₁₋₈ alkyl, optionally substituted C₁₋₈ alkoxy-C₁₋₈ alkyl,and a second group represented by R₅ in which R₆ is optionallysubstituted C₁₋₈ alkyl or optionally substituted C₁₋₈ alkoxy-C₁₋₈ alkyl,R₇ is selected from H and optionally substituted C₁₋₈ alkyl, and R₈ isselected from optionally substituted C₁₋₈ alkyl, optionally substitutedC₁₋₈ alkoxy-C₁₋₈ alkyl, optionally substituted C₁₋₈ alkyl sulfonyl orcarbonyl, and optionally substituted phenyl sulfonyl or carbamoyl.

European Patent Publication EP 0 247 737, the disclosure of which istotally incorporated herein by reference, discloses a thermal transferprinting sheet suitable for use in a thermal transfer printing process,especially for the conversion of a digital image into a visible print,comprising a substrate having a coating comprising a dye of the formula

wherein Ring A is unsubstituted or carries, in the 2- or 4-position withrespect to the azo link, at least one group selected from —CX₃, X¹, CN,NO₂, —OCO.Y, —CO.Y, —CO.H, —OSO₂.Y, and —SO₂.Y, provided that A issubstituted when Z is CH₃ and R is C₂₋₄-alkyl; X and X¹ are eachindependently halogen; Y is selected from R¹, —OR¹, SR¹, and —NR¹R²; R¹is selected from C₁₋₁₂-alkyl, C₁₋₁₂-alkyl interrupted by one or twogroups selected from —O—, —CO—, O.CO—, and —CO.O—, C₃₋₇-cycloalkyl,mono- or bi-cyclic aryl, and C₁₋₃-alkylene attached to an adjacentcarbon atom on Ring A; R² is selected from H, C₁₋₁₂-alkyl,C₃₋₇-cycloalkyl, and mono- or bi-cyclic aryl; Z is C₁₋₁₂-alkyl orphenyl; and R is selected from C₂₋₁₂-alkyl unbranched in thealpha-position, C₂₋₁₂-alkyl unbranched in alpha-position and interruptedby one or two groups selected from —O—, —CO—, O.CO—, and —CO.O—, phenyl,C₁₋₄-alkylphenyl, biphenyl, and biphenyl interrupted by a group selectedfrom —O—, —CO—, O.CO—, and —CO.O—, each of which is free from hydrogenatoms capable of intermolecular hydrogen bonding.

U.S. Pat. No. 5,041,413 (Evans et al.), the disclosure of which istotally incorporated herein by reference, discloses a yellow dye-donorelement for thermal dye transfer comprises a support having thereon adye layer comprising a mixture of yellow dyes dispersed in a polymericbinder, at least one of the yellow dyes having the formula

wherein: each R¹ independently represents a substituted or unsubstitutedalkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group offrom about 5 to about 7 carbon atoms; a substituted or unsubstitutedallyl group; an aryl group of from about 6 to about 10 carbon atoms; ahetaryl group of from 5 to 10 atoms; acyl; arylsulfonyl; aminocarbonyl;aminosulfonyl; fluorosulfonyl; halogen; nitro; alkylthio; or arylthio;or any two adjacent R¹'s together represent the atoms necessary to forma 5- or 6-membered fused ring; n represents an integer from 0-4; R²represents hydrogen; a substituted or unsubstituted alkyl, cycloalkyl,allyl, aryl or hetaryl group as described above for R¹; cyano; acyl;alkylsulfonyl; arylsulfonyl; or alkoxycarbonyl; Z represents cyano;alkoxycarbonyl; acyl; nitro; arylsulfonyl or alkylsulfonyl; Y representshydrogen; a substituted or unsubstituted alkyl, cycloalkyl, allyl, arylor hetaryl group as described above for R¹; amino; alkylamino;arylamino; acylamino; or sulfonylamino; and at least one of the other ofthe dyes having the formula

wherein R³ represents the same groups as R¹ above; R⁴ and R⁵ eachindependently represents hydrogen, R³; cyano; acyloxy; alkoxy of 1 toabout 6 carbon atoms; halogen; or alkoxycarbonyl; or any two of R³, R⁴and R⁵ together represent the atoms necessary to complete a 5- to7-membered ring; R⁶ represents the same groups as R³; G represents asubstituted or unsubstituted alkyl, cycloalkyl or allyl group asdescribed above for R³, NR⁷R⁸ or OR⁹; R⁷ and R⁸ each independentlyrepresents hydrogen, acyl or R³, with the proviso that R⁷ and R⁸ cannotboth be hydrogen at the same time; or R⁷ and R⁸ together represent theatoms necessary to complete a 5- to 7-membered ring; R⁹ represents thesame groups as R³; X represents C(R¹⁰)(R¹¹), S, O or NR¹⁰; R¹⁰ and R¹¹each independently represents the same groups as R³; or R¹⁰ and R¹¹together represent the atoms necessary to complete a 5- to 7-memberedring; and J represents the atoms necessary to complete a 5- or6-membered ring which may be fused to another ring system.

U.S. Pat. No. 4,359,418 (Lienhard et al.), the disclosure of which istotally incorporated herein by reference, discloses azo dyestuffsulfonic acid salts of the formula

wherein A represents a carbocyclic or heterocyclic aromatic radical, Brepresents an aliphatic, cycloaliphatic or araliphatic amine, Xrepresents a hydrogen atom or a substituted or unsubstituted alkylgroup, a cycloalkyl, aralkyl or aryl group, Y represents a hydrogen orhalogen atom, a nitro, cyano, acyl, sulfonic acid, arylsulfonyl,alkoxycarbonyl group or a substituted or unsubstituted alkyl, sulfamoylor carbamoyl group, Z represents a substituted or unsubstituted alkylgroup or an aryl radical, m and n are 1 or 2; said dyestuffs saltshaving good solubility in organic solvents and functioning to colorsolutions of film forming polymers in yellow to orange shades.

German Patent Publication DE 3538517 and U.S. Pat. No. 5,037,964 (Moseret al.), the disclosures of each of which are totally incorporatedherein by reference, disclose sulfonic acid group-free basic azocompounds, which correspond in one of the possible tautomeric forms tothe formula

their preparation and their use for dyeing paper.

Japanese Patent Publication JP 03192158, the disclosure of which istotally incorporated herein by reference, discloses obtaining a yellowdye exhibiting high dyeing speed and degree of exhaustion in dyeing atextile material, leather, pulp, paper, etc., as well as excellentbrightness and fastness to water by selecting a compound wherein apyridopyridinium salt is linked to diphenylfluorene through azo groups.A cationic compound of the formula

wherein R₁ is H or 1-4C alkyl; R₂ is H, 1-4C alkyl, or alkoxy; and A⁻ isan anion which has a structure wherein a tetrazo compound, of9,9′-bis(4-anilino)fluorene is coupled with a pyridone derivative isselected as a yellow dye, which is useful for dyeing an unsized pulp orpaper (e.g. a napkin, table cloth, or sanitary paper). The dyeing withthe dye is carried out at a pH of 4-8, preferably 5-7, and at 10-50° C.,preferably 15-30° C.

British Patent Publication GB 2 008 606, the disclosure of which istotally incorporated herein by reference, discloses water-insolubleyellow monoazo dyes suitable for dyeing hydrophobic synthetic fibres,particularly polyesters, having the formula

in which X represents OR³ or NHR³, NR³R⁴ (R³, R⁴ together optionallyforming with N a ring having 5 to 6 carbon atoms), NHR⁵; R¹ represents ahydrogen atom, an alkyl having 1 to 5 carbon atoms, (CH₂)₂OH or(CH₂)₃OR₃; R² represents CN, COOR³, CONHR³, CONR³R⁴ (R³, R⁴ togetheroptionally forming with N a ring having 5 to 6 carbon atoms); R³ and R⁴represent alkyl groups having 1 to 5 carbon atoms; and R⁵ represents acycloalkyl having 5 or 6 carbon atoms. The dyes may be prepared by thereaction of

with Hal-CH₂—CO—X in which Hal represents Cl or Br.

“Preparation and Evaluation of Yellow Pigments Based on H-Pyridone andEsters of Aminoterephthalic Acid,” P. Slosar et al., CHEMagazin, Vol. 9,No. 6, pp. 8-11 (1999), the disclosure of which is totally incorporatedherein by reference, discloses yellow pigments based on H-pyridone andesters of aminoterephthalic acid wherein the color strength, brilliance(purity), and deepening of greenish shade were the larger the smalleralkyl is in the carbalkoxy group in o-position towards the azo group andthe greater alkyl is in the carbalkoxy group in m-position towards theazo group.

Of potential background interest with respect to the present inventionare the following references: U.S. Pat. No. 5,919,839; U.S. Pat. No.5,827,918; U.S. Pat. No. 4,889,560; U.S. Pat. No. 5,372,852; “Synthesis,Morphology, and Optical Properties of TetrahedralOligo(phenylenevinylene) Materials,” S. Wang et al., J. Am. Chem. Soc.,Vol. 120, p. 5695 (2000); “Syntheses of Amphiphilic Diblock CopolymersContaining a Conjugated Block and Their Self-Assembling Properties,” H.Wang et al., J. Am. Chem. Soc., Vol. 122, p. 6855 (2000); “CrystalEngineering of Conjugated Oligomers and the Spectral Signature of πStacking in Conjugated Oligomers and Polymers,” A. Koren et al., Chem.Mater., Vol. 12, p. 1519 (2000); “The Chemistry of Isatoic Anhydride,”G. M. Coppola, Synthesis, p. 505 (1980); “Isatoic Anhydride. IV.Reactions with Various Nucleophiles,” R. P. Staiger et al., J. Org.Chem., Vol. 24, p. 1214 (1959); “Investigation of the ReactionConditions for the Synthesis of 4,6-Disubstituted-3-cyano-2-pyridonesand 4-Methyl-3-cyano-6-hydroxy-2-pyridone,” D. Z. Mijin et al., J. Serb.Chem. Soc., Vol. 59, No. 12, p. 959 (1994); “Synthesis of IsoquinolineAlkaloids. II. The Synthesis and Reactions of4-Methyl-3-pyridinecarboxaldehyde and Other 4-Methyl-3-substitutedPyridines,” J. M. Bobbitt et al., J. Org. Chem., Vol. 25, p. 560 (1960);“Synthesis and Dyeing Characteristics of 5-(4-Arylazophenyl)azo-3-cyano-4-methyl-6-hydroxy-2-pyridones,” J. Kanhere et al., IndianJournal of Textile Research, Vol. 13, p. 213 (1988); “Synthesis of SomePyridone Azo Dyes from 1-Substituted 2-Hydroxy-6-pyridone Derivativesand their Colour Assessment,” C. Chen et al., Dyes and Pigments, Vol.15, p. 69 (1991); German Patent Publication DE 3543360; Japanese PatentPublication JP 2001214083; German Patent Publication DE 3505899; IndianPatent Publication 147527; European Patent Publication EP 0 524 637;European Patent Publication EP 0 529 282; European Patent Publication EP0 083 553; Japanese Patent Publication JP 2000 62327; Japanese PatentPublication JP 85152563; “Synthesis of3-Cyano-6-hydroxy-5-(2-(perfluoroalkyl)phenylazo)-2-pyridones and theirApplication for Dye Diffusion Thermal Transfer Printing,” Bull. Chem.Soc. Jpn., 1993, Vol. 66, Iss. 6, Pp. 1790-4; European PatentPublication 0 844 287; European Patent Publication 0 404 493; U.S. Pat.No. 5,902,841; U.S. Pat. No. 5,621,022; U.S. Pat. No. 5,006,170; ChinesePatent Publication CN 1115773; German Patent Publication DE 3447117;Japanese Patent Publication JP 5331382; Japanese Patent Publication JP63210169; Japanese Patent Publication JP 63199764; Japanese PatentPublication JP 63199763; Japanese Patent Publication JP 63199762;Japanese Patent Publication JP 63199761; Japanese Patent Publication JP63199760; Japanese Patent Publication JP 63071392; Japanese PatentPublication JP 61181865; Japanese Patent Publication JP 61036366;Japanese Patent Publication JP 60152563; Japanese Patent Publication JP60112862; Japanese Patent Publication JP 60112861; Japanese PatentPublication JP 58149953; Japanese Patent Publication JP 56092961;Japanese Patent Publication JP 56026957; Japanese Patent Publication JP55099958; Japanese Patent Publication JP 96 11443 (JP8011443); JapanesePatent Publication JP 93169849 (JP5169849); Japanese Patent PublicationJP 93 51536 (JP5051536); Japanese Patent Publication JP 90185569(JP2185569); European Patent Publication 0 319 234; European PatentPublication 0 314 002; European Patent Publication 0 302 401; U.S. Pat.No. 4,734,349; Japanese Patent Publication JP 87290762 (JP62290762);Japanese Patent Publication JP 86244595 (JP61244595); Indian PatentPublication IN 147868; Spanish Patent Publication 475254 (Equivalent ofItalian Patent Publication IT 1088895); German Patent Publication DE2727809; “Colour and Constitution of Azo Dyes Derived from2-Thioalkyl-4,6-Diaminopyrimidines and3-Cyano-1,4-dimethyl-6-hydroxy-2-pyridone as Coupling Components,” L.Cheng et al., Dyes and Pigments, Vol. 7, No. 5, pp. 373-388 (1986);European Patent Publication 1 168 046; U.S. Pat. No. 4,644,058; JapanesePatent Publication JP 63039380; Japanese Patent Publication JP 54102328;Japanese Patent Publication JP 54070337; “Trends in Modern DyeChemistry. Part 10,” N. R. Ayyangar and K. V. Srinivasan, Colourage,Vol. 37, No. 2, pp. 29-30 (Jan. 16, 1990); European Patent PublicationEP 0 172 283; Japanese Patent Publication JP 05169854; Japanese PatentPublication JP 04292988; Japanese Patent Publication JP 63161060;Japanese Patent Publication JP 61244595; Korean Patent Publication KR119563; European Patent Publication EP 0 142 863; European PatentPublication EP 0 023 770; Japanese Patent Publication JP 00239549(JP2000239549); Japanese Patent Publication JP 11269402; Japanese PatentPublication JP 09041267; Japanese Patent Publication JP 08039941; U.S.Pat. No. 4,994,564; Japanese Patent Publication JP 06294909; JapanesePatent Publication JP 06122829; Japanese Patent Publication JP 05255602;Japanese Patent Publication JP 05051536; Japanese Patent Publication JP04235093; European Patent Publication EP 0 468 647; European PatentPublication EP 0 063 275; U.S. Pat. No. 4,216,145; and German PatentPublication DE 2606506; the disclosures of each of which are totallyincorporated herein by reference.

While known compositions and processes are suitable for their intendedpurposes, a need remains for new yellow colorant compositions. Inaddition, a need remains for yellow colorant compositions particularlysuitable for use in phase change inks. Further, a need remains foryellow colorants with desirable thermal stability. Additionally, a needremains for yellow colorants that exhibit minimal undesirablediscoloration when exposed to elevated temperatures. There is also aneed for yellow colorants that exhibit a desirable brilliance. Inaddition, there is a need for yellow colorants that exhibit a desirablehue. Further, there is a need for yellow colorants that are of desirablechroma. Additionally, there is a need for yellow colorants that havedesirably high lighffastness characteristics. A need also remains foryellow colorants that have a desirably pleasing color. In addition, aneed remains for yellow colorants that exhibit desirable solubilitycharacteristics in phase change ink carrier compositions. Further, aneed remains for yellow colorants that enable phase change inks to bejetted at temperatures of over 135° C. while maintaining thermalstability. Additionally, a need remains for yellow colorants that enablephase change inks that generate images with low pile height. There isalso a need for yellow colorants that enable phase change inks thatgenerate images that approach lithographic thin image quality. Inaddition, there is a need for yellow colorants that exhibit oxidativestability. Further, there is a need for yellow colorants that do notprecipitate from phase change ink carriers. Additionally, there is aneed for yellow colorants that do not, when included in phase changeinks, diffuse into adjacently printed inks of different colors. A needalso remains for yellow colorants that do not leach from media such asphase change ink carriers into tape adhesives, paper, or the like. Inaddition, a need remains for yellow colorants that, when incorporatedinto phase change inks, do not lead to clogging of a phase change inkjet printhead. Further, there is a need for yellow colorants that enablephase change inks that generate images with sharp edges that remainsharp over time. Additionally, there is a need for yellow colorants thatenable phase change inks that generate images which retain their highimage quality in warm climates. Further, there is a need for yellowcolorants that enable phase change inks that generate images ofdesirably high optical density. Additionally, there is a need for yellowcolorants that, because of their good solubility in phase change inkcarriers, enable the generation of images of low pile height without theloss of desirably high optical density. A need also remains for yellowcolorants that enable the use of substantially reduced amounts ofcolorant in, for example, an ink without decreasing the color and thespectral properties (L*a*b*) of the ink or jeopardizing the opticaldensity or color of the prints generated with the ink. In addition, aneed remains for yellow colorants that enable cost-effective inks.

SUMMARY

Disclosed herein is a compound comprising three or more moieties of theformula

wherein (A) each R₁, independently of the others, is (i) an alkyl oralkylene group, (ii) an aryl or arylene group, (iii) an arylalkyl orarylalkylene group, (iv) an alkylaryl or alkylarylene group, (v) a silylor silylene group, or (vi) a siloxy group, (B) each R₂, independently ofthe others, is (i) an alkyl or alkylene group, (ii) an aryl or arylenegroup, (iii) an arylalkyl or arylalkylene group, (iv) an alkylaryl oralkylarylene group, (v) a silyl or silylene group, (vi) a siloxy group,or (vii) a group of the formula

wherein r and s are each, independently of the other, integersrepresenting a number of repeat —CH₂— groups, (C) each R₃, independentlyof the others, is (i) an alkyl group, (ii) an aryl group, (iii) anarylalkyl group, or (iv) an alkylaryl group, (D) each X, independentlyof the others, is (i) a direct bond, (ii) an oxygen atom, (iii) a sulfuratom, (iv) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and (E) each Z,independently of the others, is (i) a hydrogen atom, (ii) a halogenatom, (iii) a nitro group, (iv) an alkyl group, (v) an aryl group, (vi)an arylalkyl group, (vii) an alkylaryl group, (viii) a group of theformula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, a silyl group, or a siloxy group, (ix) a sulfonyl groupof the formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group,an aryl group, an arylalkyl group, an alkylaryl group, a silyl group, ora siloxy group, or (x) a phosphoryl group of the formula —PO₃R₉₀ whereinR₉₀ is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, a silyl group, or a siloxy group; saidmoieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer. Also disclosed herein is a phase change inkcomprising a phase change ink carrier and a colorant compound comprisingthree or more moieties of the formula

said moieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer.

DETAILED DESCRIPTION

Disclosed herein are colorant compounds containing three or moremoieties of the formula

These moieties are linked by a central atom or monomeric group of atomsor bonded to an oligomer or polymer. For example, a moiety of thisformula can be linked to a central atom or group of atoms through the R₁group, in which case the R₁ group is divalent or polyvalent, as follows:

Or, for example, a moiety of this formula can be linked to a centralatom or group of atoms through the R₂ group, in which case the R₂ groupis divalent or polyvalent, as follows:

The moieties can be bonded to a single central atom, with four examplesof such types of compounds being

The moieties can also be linked to different atoms in a monomericcentral group of atoms. The central group of atoms can be a smallmolecule, such as ethylene or propylene or benzene, or, if desired, alarger molecule. In addition, the central group of atoms can be anoligomer or a polymer. The central molecule can be selected forcompatibility with the other components with which the colorant is to beadmixed, if any, or for the purpose for which the colorant is to beused. For example, when the colorant is to be used in a phase changeink, in one specific embodiment polymers or oligomers with about 20repeat monomer units or fewer can be employed. In another embodiment,polymers or oligomers with from about 10 to about 20 repeat monomerunits are employed.

The chromogen moieties are of the general formula

In this formula, each R₁, independently of the other R₁ groups in otherchromogen moieties attached to the central atom or group of atoms, is(i) an alkyl or alkylene group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkyl and alkylenegroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl or alkylene group), in one embodiment with at least 1 carbonatom, in another embodiment with at least about 8 carbon atoms, in yetanother embodiment with at least about 10 carbon atoms, in still anotherembodiment with at least about 12 carbon atoms, in another embodimentwith at least about 14 carbon atoms, in yet another embodiment with atleast about 16 carbon atoms, in still another embodiment with at leastabout 18 carbon atoms, in another embodiment with at least about 20carbon atoms, in yet another embodiment with at least about 22 carbonatoms, in still another embodiment with at least about 24 carbon atoms,in another embodiment with at least about 26 carbon atoms, in yetanother embodiment with at least about 28 carbon atoms, in still anotherembodiment with at least about 30 carbon atoms, in another embodimentwith at least about 32 carbon atoms, in yet another embodiment with atleast about 34 carbon atoms, and in still another embodiment with atleast about 36 carbon atoms, and in one embodiment with no more thanabout 200 carbon atoms, in another embodiment with no more than about100 carbon atoms, in yet another embodiment with no more than about 75carbon atoms, in still another embodiment with no more than about 60carbon atoms, in another embodiment with no more than about 50 carbonatoms, and in yet another embodiment with no more than about 40 carbonatoms, although the number of carbon atoms can be outside of theseranges, (ii) an aryl or arylene group (including unsubstituted andsubstituted aryl and arylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in the aryl or arylene group), in one embodimentwith at least about 6 carbon atoms, in another embodiment with at leastabout 10 carbon atoms, in yet another embodiment with at least about 13carbon atoms, in still another embodiment with at least about 14 carbonatoms, in another embodiment with at least about 16 carbon atoms, in yetanother embodiment with at least about 17 carbon atoms, in still anotherembodiment with at least about 18 carbon atoms, in another embodimentwith at least about 19 carbon atoms, in yet another embodiment with atleast about 20 carbon atoms, in still another embodiment with at leastabout 21 carbon atoms, in another embodiment with at least about 22carbon atoms, and in yet another embodiment with at least about 23carbon atoms, and in one embodiment with no more than about 100 carbonatoms, in another embodiment with no more than about 75 carbon atoms,and in yet another embodiment with no more than about 50 carbon atoms,although the number of carbon atoms can be outside of these ranges,(iii) an arylalkyl or arylalkylene group (including unsubstituted andsubstituted arylalkyl and arylalkylene groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either or both of the aryl portionand the alkyl portion of the arylalkyl or arylalkylene group), in oneembodiment with at least about 7 carbon atoms, in another embodimentwith at least about 8 carbon atoms, in another embodiment with at leastabout 10 carbon atoms, in yet another embodiment with at least about 12carbon atoms, in still another embodiment with at least about 14 carbonatoms, in another embodiment with at least about 16 carbon atoms, in yetanother embodiment with at least about 18 carbon atoms, in still anotherembodiment with at least about 20 carbon atoms, in another embodimentwith at least about 22 carbon atoms, in yet another embodiment with atleast about 24 carbon atoms, in still another embodiment with at leastabout 26 carbon atoms, in another embodiment with at least about 28carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in still another embodiment with at least about 32 carbon atoms,in another embodiment with at least about 34 carbon atoms, in yetanother embodiment with at least about 36 carbon atoms, in anotherembodiment with at least about 38 carbon atoms, in yet anotherembodiment with at least about 40 carbon atoms, and in still anotherembodiment with at least about 42 carbon atoms, and in one embodimentwith no more than about 200 carbon atoms, in another embodiment with nomore than about 100 carbon atoms, and in yet another embodiment with nomore than about 44 carbon atoms, although the number of carbon atoms canbe outside of these ranges, (iv) an alkylaryl or alkylarylene group(including unsubstituted and substituted alkylaryl and alkylarylenegroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thealkylaryl or alkylarylene group), in one embodiment with at least about7 carbon atoms, in another embodiment with at least about 8 carbonatoms, in another embodiment with at least about 10 carbon atoms, in yetanother embodiment with at least about 12 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 16 carbon atoms, in yet another embodiment with atleast about 18 carbon atoms, in still another embodiment with at leastabout 20 carbon atoms, in another embodiment with at least about 22carbon atoms, in yet another embodiment with at least about 24 carbonatoms, in still another embodiment with at least about 26 carbon atoms,in another embodiment with at least about 28 carbon atoms, in yetanother embodiment with at least about 30 carbon atoms, in still anotherembodiment with at least about 32 carbon atoms, in another embodimentwith at least about 34 carbon atoms, in yet another embodiment with atleast about 36 carbon atoms, in another embodiment with at least about38 carbon atoms, in yet another embodiment with at least about 40 carbonatoms, and in still another embodiment with at least about 42 carbonatoms, and in one embodiment with no more than about 200 carbon atoms,in another embodiment with no more than about 100 carbon atoms, and inyet another embodiment with no more than about 44 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, (v) a silylor silylene group (including unsubstituted and substituted silyl andsilylene groups, and including polysilylene groups, in one embodimentwith from 2 to about 100 repeat silylene units, although the number ofrepeat units can be outside of this range), or (vi) a siloxy group(including unsubstituted and substituted siloxy groups, and includingpolysiloxane groups, in one embodiment with from 2 to about 200 repeatsiloxane units, although the number of repeat units can be outside ofthis range), wherein the substituents on the substituted alkyl,alkylene, aryl, arylene, arylalkyl, arylalkylene, alkylaryl,alkylarylene, silyl, silylene, and siloxane groups can be (but are notlimited to) hydroxy groups, halogen atoms, cyano groups, ether groups,aldehyde groups, ketone groups, carboxylic acid groups, ester groups,amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups,sulfonate groups, sulfide groups, sulfoxide groups, phosphate groups,nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfonegroups, acyl groups, acid anhydride groups, azide groups, cyanatogroups, isocyanato groups, thiocyanato groups, isothiocyanato groups,mixtures thereof, and the like, wherein the substituents on the silyl,silylene, and siloxy groups can also be alkyl groups, aryl groups,arylalkyl groups, and alkylaryl groups, wherein two or more substituentscan be joined together to form a ring. Since hetero atoms can be presentin the alkyl, alkylene, aryl, arylene, arylalkyl, arylalkylene,alkylaryl, and alkylarylene groups, these groups also include alkoxy,alkyleneoxy, aryloxy, aryleneoxy, arylalkyloxy, arylalkyleneoxy,alkylaryloxy, alkylaryleneoxy, and the like; in addition, these groupsalso include polyalkyleneoxy groups, including (but not limited to)those wherein the alkyl portion of the repeat alkyleneoxy group has from1 to about 12 carbon atoms, although the number of carbon atoms can beoutside of these ranges, such as a polyethyleneoxy group, apolypropyleneoxy group, a polybutyleneoxy group, or the like, andwherein the number of repeat alkyleneoxy groups is from about 2 to about50, polyaryleneoxy groups, including (but not limited to) those whereinthe aryl portion of the repeat aryleneoxy group has from about 6 toabout 14 carbon atoms, such as a polyphenyleneoxy group, apolynaphthaleneoxy group, a polyphenanthreneoxy group, or the like, andwherein the number of repeat aryleneoxy groups is from about 2 to about20, polyarylalkyleneoxy groups, including (but not limited to) thosewherein the arylalkyl portion of the repeat arylalkyleneoxy group hasfrom about 7 to about 50 carbon atoms, such as a polybenzyleneoxy group,a polyphenylethyleneoxy group, or the like, and wherein the number ofrepeat arylalkyleneoxy groups is from about 2 to about 20,polyalkylaryleneoxy groups, including (but not limited to) those whereinthe alkylaryl portion of the repeat alkylaryleneoxy group has from about7 to about 50 carbon atoms, such as a polytolueneoxy group or the like,and wherein the number of repeat alkylaryleneoxy groups is from about 2to about 20, and the like. Further, since hetero atoms can be present inthese groups, these groups also include heterocyclic groups.

Some specific examples of suitable monovalent R₁ groups include (but arenot limited to) methyl, of the formula —CH₃, ethyl, of the formula—C₂H₅, n-octyl, of the formula —(CH₂)₇CH₃, stearyl, of the formula—(CH₂)₁₇CH₃, menthyl, of the formula

wherein the “S” indicates that the ring is saturated as opposed to beingaromatic, branched saturated hydrocarbon groups containing 18 carbonatoms, of the general formula

wherein q is an integer of from about 10 to about 15, p is an integer offrom 0 to about 3, and the sum of p+q=15, such as isostearyl, oleyl, ofthe formula

2-octyldodecyl, of the formula

cholesteryl, of the formula

abietyl, including groups of the formula

as well as hydrogenated and dehydrogenated isomers of the above formulathat are also derivatives of the rosin-derived natural product abieticacid, such as didehydroabietyl and the like, 2-ethylhexyl, of theformula

(1-oxypropyl)-2-octyldodecane, of the formula

and the like. Some specific examples of suitable divalent R₁ groupsinclude (but are not limited to) n-hexanediyl, of the formula —(CH₂)₆—,n-octanediyl, of the formula —(CH₂)₈—, n-decanediyl, of the formula—(CH₂)₁₀—, n-dodecanediyl, of the formula —(CH₂)₁₂—,3-methyl-1,5-pentanediyl, of the formula

1,4-cyclohexanedimethylene, of the formula (which is not intended to belimited to any particular stereochemistry and includes all cis and transisomers)

4,4′-isopropylidenedicyclohexanediyl, of the formula (which is notintended to be limited to any particular stereochemistry and includesall cis and trans isomers)

4,4′-bicyclohexyanediyl, of the formula (which is not intended to belimited to any particular stereochemistry and includes all cis and transisomers)

a branched alkylene group having 36 carbon atoms, including isomers ofthe formula

and other branched alkylene isomers (which may include unsaturations andcyclic groups), 4,8-bis(methylene)tricyclo(5210^(2,6))decanediyl, of theformula (which is not intended to be limited to any particularstereochemistry and includes all cis and trans isomers)

and the like.

In the chromogen moieties of the above formula, each R₂, independentlyof the other R₂ groups in other chromogen moieties attached to thecentral atom or group of atoms, is (i) an alkyl or alkylene group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl and alkylene groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the alkyl or alkylenegroup), in one embodiment with at least 1 carbon atom, in anotherembodiment with at least about 8 carbon atoms, in yet another embodimentwith at least about 10 carbon atoms, in still another embodiment with atleast about 12 carbon atoms, in another embodiment with at least about14 carbon atoms, in yet another embodiment with at least about 16 carbonatoms, in still another embodiment with at least about 18 carbon atoms,in another embodiment with at least about 20 carbon atoms, in yetanother embodiment with at least about 22 carbon atoms, in still anotherembodiment with at least about 24 carbon atoms, in another embodimentwith at least about 26 carbon atoms, in yet another embodiment with atleast about 28 carbon atoms, in still another embodiment with at leastabout 30 carbon atoms, in another embodiment with at least about 32carbon atoms, in yet another embodiment with at least about 34 carbonatoms, and in still another embodiment with at least about 36 carbonatoms, and in one embodiment with no more than about 200 carbon atoms,in another embodiment with no more than about 100 carbon atoms, in yetanother embodiment with no more than about 75 carbon atoms, in stillanother embodiment with no more than about 60 carbon atoms, in anotherembodiment with no more than about 50 carbon atoms, and in yet anotherembodiment with no more than about 40 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (ii) an aryl or arylenegroup (including unsubstituted and substituted aryl and arylene groups,and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the aryl orarylene group), in one embodiment with at least about 6 carbon atoms, inanother embodiment with at least about 10 carbon atoms, in yet anotherembodiment with at least about 13 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 16 carbon atoms, in yet another embodiment with atleast about 17 carbon atoms, in still another embodiment with at leastabout 18 carbon atoms, in another embodiment with at least about 19carbon atoms, in yet another embodiment with at least about 20 carbonatoms, in still another embodiment with at least about 21 carbon atoms,in another embodiment with at least about 22 carbon atoms, and in yetanother embodiment with at least about 23 carbon atoms, and in oneembodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 75 carbon atoms, and in yet anotherembodiment with no more than about 50 carbon atoms, although the numberof carbon atoms can be outside of these ranges, (iii) an arylalkyl orarylalkylene group (including unsubstituted and substituted arylalkyland arylalkylene groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the aryl portion and the alkylportion of the arylalkyl or arylalkylene group), in one embodiment withat least about 7 carbon atoms, in another embodiment with at least about8 carbon atoms, in another embodiment with at least about 10 carbonatoms, in yet another embodiment with at least about 12 carbon atoms, instill another embodiment with at least about 14 carbon atoms, in anotherembodiment with at least about 16 carbon atoms, in yet anotherembodiment with at least about 18 carbon atoms, in still anotherembodiment with at least about 20 carbon atoms, in another embodimentwith at least about 22 carbon atoms, in yet another embodiment with atleast about 24 carbon atoms, in still another embodiment with at leastabout 26 carbon atoms, in another embodiment with at least about 28carbon atoms, in yet another embodiment with at least about 30 carbonatoms, in still another embodiment with at least about 32 carbon atoms,in another embodiment with at least about 34 carbon atoms, in yetanother embodiment with at least about 36 carbon atoms, in anotherembodiment with at least about 38 carbon atoms, in yet anotherembodiment with at least about 40 carbon atoms, and in still anotherembodiment with at least about 42 carbon atoms, and in one embodimentwith no more than about 200 carbon atoms, in another embodiment with nomore than about 100 carbon atoms, and in yet another embodiment with nomore than about 44 carbon atoms, although the number of carbon atoms canbe outside of these ranges, (iv) an alkylaryl or alkylarylene group(including unsubstituted and substituted alkylaryl and alkylarylenegroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thealkylaryl or alkylarylene group), in one embodiment with at least about7 carbon atoms, in another embodiment with at least about 8 carbonatoms, in another embodiment with at least about 10 carbon atoms, in yetanother embodiment with at least about 12 carbon atoms, in still anotherembodiment with at least about 14 carbon atoms, in another embodimentwith at least about 16 carbon atoms, in yet another embodiment with atleast about 18 carbon atoms, in still another embodiment with at leastabout 20 carbon atoms, in another embodiment with at least about 22carbon atoms, in yet another embodiment with at least about 24 carbonatoms, in still another embodiment with at least about 26 carbon atoms,in another embodiment with at least about 28 carbon atoms, in yetanother embodiment with at least about 30 carbon atoms, in still anotherembodiment with at least about 32 carbon atoms, in another embodimentwith at least about 34 carbon atoms, in yet another embodiment with atleast about 36 carbon atoms, in another embodiment with at least about38 carbon atoms, in yet another embodiment with at least about 40 carbonatoms, and in still another embodiment with at least about 42 carbonatoms, and in one embodiment with no more than about 200 carbon atoms,in another embodiment with no more than about 100 carbon atoms, and inyet another embodiment with no more than about 44 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, (v) a silylor silylene group (including unsubstituted and substituted silyl andsilylene groups, and including polysilylene groups, in one embodimentwith from 2 to about 100 repeat silylene units, although the number ofrepeat units can be outside of this range), (vi) a siloxy group(including unsubstituted and substituted siloxane groups, and includingpolysiloxane groups, in one embodiment with from 2 to about 200 repeatsiloxane units, although the number of repeat units can be outside ofthis range), or (vii) a group of the formula

wherein r is an integer representing the number of repeat —CH₂— groups,in one embodiment being at least 1, in another embodiment at least about5, and in yet another embodiment at least about 10, and in oneembodiment being no more than about 100, in another embodiment no morethan about 50, and in yet another embodiment no more than about 25,although the value of r can be outside of these ranges, and wherein s isan integer representing the number of repeating —CH₂— groups, in oneembodiment being at least 1, in another embodiment at least about 5, andin yet another embodiment at least about 10, and in one embodiment beingno more than about 100, in another embodiment no more than about 50, andin yet another embodiment no more than about 25, although the value of scan be outside of these ranges, wherein the substituents on thesubstituted alkyl, alkylene, aryl, arylene, arylalkyl, arylalkylene,alkylaryl, alkylarylene, silyl, silylene, and siloxy groups are hydroxygroups, halogen atoms, cyano groups, ether groups, aldehyde groups,ketone groups, carboxylic acid groups, ester groups, amide groups,carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups,sulfide groups, sulfoxide groups, phosphate groups, nitrile groups,mercapto groups, nitro groups, nitroso groups, sulfone groups, acylgroups, acid anhydride groups, azide groups, cyanato groups, isocyanatogroups, thiocyanato groups, isothiocyanato groups, mixtures thereof, andthe like, wherein the substituents on the silyl and siloxy groups canalso be alkyl groups, aryl groups, arylalkyl groups, and alkylarylgroups, wherein two or more substituents can be joined together to forma ring. Since hetero atoms can be present in the alkyl, alkylene, aryl,arylene, arylalkyl, arylalkylene, alkylaryl, and alkylarylene groups,these groups also include alkoxy, alkyleneoxy, aryloxy, aryleneoxy,arylalkyloxy, arylalkyleneoxy, alkylaryloxy, alkylaryleneoxy, and thelike; in addition, these groups also include polyalkyleneoxy groups,including (but not limited to) those wherein the alkyl portion of therepeat alkyleneoxy group has from 1 to about 12 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, such as apolyethyleneoxy group, a polypropyleneoxy group, a polybutyleneoxygroup, or the like, and wherein the number of repeat alkyleneoxy groupsis from about 2 to about 50, polyaryleneoxy groups, including (but notlimited to) those wherein the aryl portion of the repeat aryleneoxygroup has from about 6 to about 14-carbon atoms, such as apolyphenyleneoxy group, a polynaphthaleneoxy group, apolyphenanthreneoxy group, or the like, and wherein the number of repeataryleneoxy groups is from about 2 to about 20, polyarylalkyleneoxygroups, including (but not limited to) those wherein the arylalkylportion of the repeat arylalkyleneoxy group has from about 7 to about 50carbon atoms, such as a polybenzyleneoxy group, a polyphenylethyleneoxygroup, or the like, and wherein the number of repeat arylalkyleneoxygroups is from about 2 to about 20, polyalkylaryleneoxy groups,including (but not limited to) those wherein the alkylaryl portion ofthe repeat alkylaryleneoxy group has from about 7 to about 50 carbonatoms, such as a polytolueneoxy group or the like, and wherein thenumber of repeat alkylaryleneoxy groups is from about 2 to about 20, andthe like. Further, since hetero atoms can be present in these groups,these groups also include heterocyclic groups.

Some specific examples of suitable monovalent R₂ groups include (but arenot limited to) ethyl, of the formula —CH₂CH₃, n-butyl, of the formula—(CH₂)₃CH₃, n-octyl, of the formula —(CH₂)₇CH₃, n-decyl, of the formula—(CH₂)₉CH₃, n-dodecyl, of the formula —(CH₂)₁₁CH₃, n-tetradecyl, of theformula —(CH₂)₁₃CH₃, cetyl, of the formula —(CH₂)₁₅CH₃, stearyl, of theformula —(CH₂)₁₇CH₃, 2-ethylhexyl, of the formula

abietyl, including groups of the formula

as well as hydrogenated and dehydrogenated isomers of the above formulathat are also derivatives of the rosin-derived natural product abieticacid, such as didehydroabietyl and the like, 3-propyl octadecanoyl, ofthe formula

2,2-dimethyl-1,3-dioxolane-4-methylene, of the formula

and the like. Some specific examples of suitable divalent R₂ groupsinclude (but are not limited to) n-hexanediyl, of the formula —(CH₂)₆—,n-octanediyl, of the formula —(CH₂)₈—, n decanediyl, of the formula—(CH₂)₁₀—, n-dodecanediyl, of the formula —(CH₂)₁₂—,2-methyl-1,5-pentanediyl, of the formula

butane-1,4-di(oxypropyl), of the formula—CH₂CH₂CH₂—O—CH₂CH₂CH₂CH₂—O—CH₂CH₂CH₂—, 1,3-cyclohexanedimethylene, ofthe formula (which is not intended to be limited to any particularstereochemistry and includes all cis and trans isomers)

dicyclohexylmethane-4,4′-diyl, of the formula (which is not intended tobe limited to any particular stereochemistry and includes all cis andtrans isomers)

4,8-bis(methylene)tricyclo(5210^(2,6))decanediyl, of the formula (whichis not intended to be limited to any particular stereochemistry andincludes all cis and trans isomers)

a branched alkylene group having 36 carbon atoms, including isomers ofthe formula

and other branched isomers (which may include unsaturations and cyclicgroups), a branched alkylene diester group having 36 carbon atoms,including isomers of the formula

and other branched isomers (which may include unsaturations and cyclicgroups), and the like.

In the chromogen moieties of the above formula, each R₃, independentlyof the other R₃ groups in other chromogen moieties attached to thecentral atom or group of atoms, is (i) an alkyl group (including linear,branched, saturated, unsaturated, cyclic, unsubstituted, and substitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least 1 carbonatom, and in one embodiment with no more than about 100 carbon atoms, inanother embodiment with no more than about 10 carbon atoms, and in yetanother embodiment with no more than about 5 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (ii) an arylgroup (including unsubstituted and substituted aryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the aryl group), in oneembodiment with at least about 6 carbon atoms, and in one embodimentwith no more than about 100 carbon atoms, and in another embodiment withno more than about 10 carbon atoms, although the number of carbon atomscan be outside of these ranges, (iii) an arylalkyl group (includingunsubstituted and substituted arylalkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the arylportion and the alkyl portion of the arylalkyl group), in one embodimentwith at least about 7 carbon atoms, and in one embodiment with no morethan about 100 carbon atoms, and in another embodiment with no more thanabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, or (iv) an alkylaryl group (includingunsubstituted and substituted alkylaryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in either or both of the arylportion and the alkyl portion of the alkylaryl group), in one embodimentwith at least about 7 carbon atoms, and in one embodiment with no morethan about 100 carbon atoms, and in another embodiment with no more thanabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, wherein the substituents on the substitutedalkyl, aryl, arylalkyl, and alkylaryl groups can be (but are not limitedto) hydroxy groups, halogen atoms, amine groups, imine groups, ammoniumgroups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ester groups, amide groups, carbonyl groups, thiocarbonylgroups, sulfate groups, sulfonate groups, sulfide groups, sulfoxidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, sulfone groups,acyl groups, acid anhydride groups, azide groups, cyanato groups,isocyanato groups, thiocyanato groups, isothiocyanato groups, mixturesthereof, and the like, wherein two or more substituents can be joinedtogether to form a ring. Since hetero atoms can be present in the alkyl,aryl, arylalkyl, and alkylaryl groups, these groups also include alkoxy,aryloxy, arylalkyloxy, alkylaryloxy, and the like; in addition, thesegroups also include polyalkyleneoxy groups, polyaryleneoxy groups,polyarylalkyleneoxy groups, polyalkylaryleneoxy groups, and the like.Further, since hetero atoms can be present in these groups, these groupsalso include heterocyclic groups.

Some specific examples of suitable R₃ groups include methyl (—CH₃),linear alkyl groups of the formula —(CH₂)_(C)CH₃ wherein c is an integerof 1, 2, 3, 4, 5, 6, 7, 8, or 9, and the like.

In the chromogen moieties of the above formula, each X, independently ofthe other X moieties in other chromogen moieties attached to the centralatom or group of atoms, is (i) a direct bond, (ii) an oxygen atom, (iii)a sulfur atom, (iv) a group of the formula —NR₄₀— wherein R₄₀ is ahydrogen atom, an alkyl group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylgroup), in one embodiment with at least 1 carbon atom, in anotherembodiment with at least about 2 carbon atoms, and in yet anotherembodiment with at least about 4 carbon atoms, and in one embodimentwith no more than about 50 carbon atoms, in another embodiment with nomore than about 20 carbon atoms, and in yet another embodiment with nomore than about 12 carbon atoms, although the number of carbon atoms canbe outside of these ranges, an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about6 carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 20 carbon atoms,and in yet another embodiment with no more than about 10 carbon atoms,although the number of carbon atoms can be outside of these ranges, anarylalkyl group (including substituted and unsubstituted arylalkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thearylalkyl group), in one embodiment with at least about 7 carbon atoms,and in one embodiment with no more than about 100 carbon atoms, inanother embodiment with no more than about 50 carbon atoms, and in yetanother embodiment with no more than about 20 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, or an alkylarylgroup (including substituted alkylaryl and unsubstituted groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the aryl portion and the alkyl portion of the arylalkyl group),in one embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 100 carbon atoms, in anotherembodiment with no more than about 50 carbon atoms, and in yet anotherembodiment with no more than about 20 carbon atoms, although the numberof carbon atoms can be outside of these ranges, or (v) a group of theformula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each, independently of the other,is a hydrogen atom, an alkyl group (including linear, branched,saturated, unsaturated, cyclic, unsubstituted, and substituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, inanother embodiment with at least about 2 carbon atoms, and in yetanother embodiment with at least about 4 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 20 carbon atoms, and in yet anotherembodiment with no more than about 12 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingsubstituted and unsubstituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least about 6 carbon atoms, and in one-embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 20 carbon atoms, and in yet another embodiment with no more thanabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an arylalkyl group (including substituted andunsubstituted arylalkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl portion and thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 7 carbon atoms, and in one embodiment with no more than about 100carbon atoms, in another embodiment with no more than about 50 carbonatoms, and in yet another embodiment with no more than about 20 carbonatoms, although the number of carbon atoms can be outside of theseranges, or an alkylaryl group (including substituted and unsubstitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either or both of the aryl portion and the alkyl portion ofthe alkylaryl group), in one embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 100 carbon atoms,in another embodiment with no more than about 50 carbon atoms, and inyet another embodiment with no more than about 20 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges, wherein thesubstituents on the substituted alkyl, aryl, arylalkyl, and alkylarylgroups can be (but are not limited to) hydroxy groups, halogen atoms,amine groups, imine groups, ammonium groups, pyridine groups, pyridiniumgroups, ether groups, aldehyde groups, ester groups, amide groups,carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups,sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, nitrosogroups, sulfone groups, acyl-groups, acid anhydride groups, azidegroups, cyanato groups, isocyanato groups, thiocyanato groups,isothiocyanato groups, mixtures thereof, and the like, wherein two ormore substituents can be joined together to form a ring. Since heteroatoms can be present in the alkyl, aryl, arylalkyl, and alkylarylgroups, these groups also include alkoxy, aryloxy, arylalkyloxy,alkylaryloxy, and the like; in addition, these groups also includepolyalkyleneoxy groups, polyaryleneoxy groups, polyarylalkyleneoxygroups, polyalkylaryleneoxy groups, and the like. Further, since heteroatoms can be present in these groups, these groups also includeheterocyclic groups.

In the chromogen moieties of the above formula, each Z, independently ofthe other Z moieties in other chromogen moieties attached to the centralatom or group of atoms, is (i) a hydrogen atom, (ii) a halogen atom,including fluorine, chlorine, bromine, and iodine, (iii) a nitro group,(iv) an alkyl group (including linear, branched, saturated, unsaturated,cyclic, unsubstituted, and substituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, and in one embodiment with nomore than about 50 carbon atoms, in another embodiment with no more thanabout 20 carbon atoms, and in yet another embodiment with no more thanabout 10 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (v) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the aryl group), in one embodiment with at least about6 carbon atoms, and in one embodiment with no more than about 50 carbonatoms, in another embodiment with no more than about 14 carbon atoms,and in yet another embodiment with no more than about 10 carbon atoms,although the number of carbon atoms can be outside of these ranges, (vi)an arylalkyl group (including substituted and unsubstituted arylalkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thearylalkyl group), in one embodiment with at least about 7 carbon atoms,and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 15 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (vii) analkylaryl group (including substituted and unsubstituted alkylarylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thealkylaryl group), in one embodiment with at least about 7 carbon atoms,and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 15 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, (viii) a group ofthe formula

wherein R₇₀ is an alkyl group (including linear, branched, saturated,unsaturated, cyclic, unsubstituted, and substituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylgroup), in one embodiment with at least 1 carbon atom, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 20 carbon atoms, and in yet anotherembodiment with no more than about 10 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingsubstituted and unsubstituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least about 6 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 20 carbon atoms, and in yet another embodiment with no more thanabout 14 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an arylalkyl group (including substituted andunsubstituted arylalkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl portion and thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 7 carbon atoms, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 25 carbonatoms, and in yet another embodiment with no more than about 15 carbonatoms, although the number of carbon atoms can be outside of theseranges, an alkylaryl group (including substituted and unsubstitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either or both of the aryl portion and the alkyl portion ofthe alkylaryl group), in one embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 15 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, a silyl group(including unsubstituted and substituted silyl groups, and includingpolysilylene groups, in one embodiment with from 2 to about 100 repeatsilylene units, although the number of repeat units can be outside ofthis range), or a siloxy group (including unsubstituted and substitutedsiloxy groups, and including polysiloxane groups, in one embodiment withfrom 2 to about 200 repeat siloxane units, although the number of repeatunits can be outside of this range), (ix) a sulfonyl group of theformula —SO₂R₈₀, wherein R₈₀ is a hydrogen atom, an alkyl group(including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), in one embodimentwith at least 1 carbon atom, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 20carbon atoms, and in yet another embodiment with no more than about 10carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an aryl group (including substituted and unsubstitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 6 carbon atoms,and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 20 carbon atoms, and in yetanother embodiment with no more than about 14 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an arylalkylgroup (including substituted and unsubstituted arylalkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the aryl portion and the alkyl portion of the arylalkyl group),in one embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 25 carbon atoms, and in yet anotherembodiment with no more than about 15 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an alkylaryl group(including substituted and unsubstituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the alkylaryl group), in one embodimentwith at least about 7 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 25 carbon atoms, and in yet another embodiment with no more thanabout 15 carbon atoms, although the number of carbon atoms can beoutside of these ranges, a silyl group (including unsubstituted andsubstituted silyl groups, and including polysilylene groups, in oneembodiment with from 2 to about 100 repeat silylene units, although thenumber of repeat units can be outside of this range), or a siloxy group(including unsubstituted and substituted siloxy groups, and includingpolysiloxane groups, in one embodiment with from 2 to about 200 repeatsiloxane units, although the number of repeat units can be outside ofthis range), or (x) a phosphoryl group of the formula —PO₃R₉₀, whereinR₉₀ is a hydrogen atom, an alkyl group (including linear, branched,saturated, unsaturated, cyclic, unsubstituted, and substituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inone embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 20 carbon atoms, and in yet anotherembodiment with no more than about 10 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingsubstituted and unsubstituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least about 6 carbon atoms, and in one embodiment with no morethan about 50 carbon atoms, in another embodiment with no more thanabout 20 carbon atoms, and in yet another embodiment with no more thanabout 14 carbon atoms, although the number of carbon atoms can beoutside of these ranges, an arylalkyl group (including substituted andunsubstituted arylalkyl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the aryl portion and thealkyl portion of the arylalkyl group), in one embodiment with at leastabout 7 carbon atoms, and in one embodiment with no more than about 50carbon atoms, in another embodiment with no more than about 25 carbonatoms, and in yet another embodiment with no more than about 15 carbonatoms, although the number of carbon atoms can be outside of theseranges, an alkylaryl group (including substituted and unsubstitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in either or both of the aryl portion and the alkyl portion ofthe alkylaryl group), in one embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 25 carbon atoms, and in yetanother embodiment with no more than about 15 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, a silyl group(including unsubstituted and substituted silyl groups, and includingpolysilylene groups, in one embodiment with from 2 to about 100 repeatsilylene units, although the number of repeat units can be outside ofthis range), or a siloxy group (including unsubstituted and substitutedsiloxy groups, and including polysiloxane groups, in one embodiment withfrom 2 to about 200 repeat siloxane units, although the number of repeatunits can be outside of this range), wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, alkylaryl, silyl, and siloxy groupsare hydroxy groups, halogen atoms, cyano groups, ether groups, aldehydegroups, ketone groups, carboxylic acid groups, ester groups, amidegroups, carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonategroups, sulfide groups, sulfoxide groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, sulfone groups,acyl groups, acid anhydride groups, azide groups, cyanato groups,isocyanato groups, thiocyanato groups, isothiocyanato groups, mixturesthereof, and the like, wherein the substituents on the silyl and siloxygroups can also be alkyl groups, aryl groups, arylalkyl groups, andalkylaryl groups, wherein two or more substituents can be joinedtogether to form a ring. Up to 4 Z groups can be present on eachchromophore moiety. Since hetero atoms can be present in the alkyl,aryl, arylalkyl, and alkylaryl groups, these groups also include alkoxy,aryloxy, arylalkyloxy, alkylaryloxy, and the like; in addition, thesegroups also include polyalkyleneoxy groups, polyaryleneoxy groups,polyarylalkyleneoxy groups, polyalkylaryleneoxy groups, and the like.Further, since hetero atoms can be present in these groups, these groupsalso include heterocyclic groups.

Two or more of the groups R₁, Z, and X can be joined together to form aring.

Some specific examples of these colorants include

and the like.

The colorant compounds for the inks of the present invention can beprepared by any desired or effective method. For example, colorantswherein the

moieties are linked to the central atom or group of atoms or bonded to apolymer through R₁ can be prepared by formation of anthranilate moietieson the central atom or group of atoms or oligomer or polymer.Anthranilate moieties can be formed by, for example, converting primaryor secondary hydroxyl groups to anthranilate moieties by reaction of thehydroxyl groups with isatoic anhydride in the presence of a catalyst,such as 1,4-diazabicyclo(2.2.2)octane, N,N,N′,N′-tetramethylethylenediamine, or the like, and heating. The anthranilate moieties on thecentral atom or group of atoms or oligomer or polymer can then bediazotized with nitrosylsulfuric acid under cold temperature conditions,followed by coupling with the correspondingly substituted pyridone in abuffered alkaline aqueous solution under cold temperature conditions.More specifically, the correspondingly substituted polyanthranilate isfirst subjected to a diazotization reaction by dissolving it in aceticacid diluted with a solvent and, optionally, a second acid, such assulfuric acid, dodecylbenzene sulfonic acid, propionic acid,hydrochloric acid, phosphoric acid, any other acid useful for adiazotization reaction, or the like, as well as mixtures thereof. Thesolvent can be any solvent useful in a diazotization reaction, such aswater, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran,dimethoxyethane, analogous higher-boiling ether solvents, and the like,as well as mixtures thereof.

The solvent and the polyanthranilate are present in any desired oreffective relative amounts; if, for purposes of determining relativeamounts, “solvent” is defined to include whatever solvent has beenselected plus any amount of acetic acid and second acid present, thereactants are present in this combined solvent in relative amounts of inone embodiment at least about 100 grams of polyanthranilate per liter ofsolvent, in another embodiment at least about 200 grams ofpolyanthranilate per liter of solvent, and in yet another embodiment atleast about 230 grams of polyanthranilate per liter of solvent, and inone embodiment of no more than about 400 grams of polyanthranilate perliter of solvent, in another embodiment of no more than about 300 gramsof polyanthranilate per liter of solvent, and in yet another embodimentof no more than about 270 grams of polyanthranilate per liter ofsolvent, although the relative amounts can be outside of these ranges.

The acetic acid is present in any desired or effective amount, in oneembodiment at least about 1 gram of acetic acid per gram ofpolyanthranilate, in another embodiment at least about 2 grams of aceticacid per gram of polyanthranilate, and in yet another embodiment atleast about 3 grams of acetic acid per gram of polyanthranilate, and inone embodiment no more than about 10 grams of acetic acid per gram ofpolyanthranilate, in another embodiment no more than about 7 grams ofacetic acid per gram of polyanthranilate, and in yet another embodimentno more than about 5 grams of acetic acid per gram of polyanthranilate,although the relative amounts can be outside of these ranges.

When present, the optional second acid is present in any desired oreffective amount, in one embodiment at least about 0.05 gram of acid pergram of polyanthranilate, and in another embodiment at least about 0.1gram of acid per gram of polyanthranilate, and in one embodiment no morethan about 0.5 grams of acid per gram of polyanthranilate, in anotherembodiment no more than about 0.3 grams of acid per gram ofpolyanthranilate, and in yet another embodiment no more than about 0.2grams of acid per gram of polyanthranilate, although the relativeamounts can be outside of these ranges.

In the mixture comprising the selected solvent, any optional secondacid, and acetic acid, the acetic acid is present in any desired oreffective amount, in one embodiment at least about 50 percent by volumeof the mixture, in another embodiment at least about 70 percent byvolume of the mixture, in yet another embodiment at least about 75percent by volume of the mixture, and in still another embodiment atleast about 95 percent by volume of the mixture, although the relativeamount can be outside of these ranges.

Upon complete dissolution of the ingredients, the mixture is cooled, inone embodiment to a temperature of no more than about +15° C., inanother embodiment to a temperature of no more than about +10° C., inyet another embodiment to a temperature of no more than about +5° C., instill another embodiment to a temperature of no more than about +3° C.,and in one embodiment to a temperature of no lower than about −5° C.,and in another embodiment to a temperature of no lower than about −10°C., although the temperature can be outside of these ranges.

Thereafter, nitrosylsulfuric acid is added to the mixture in any desiredor effective amount, in one embodiment at least 1 mole ofnitrosylsulfuric acid per every one mole of aniline moiety in thepolyanthranilate, and in another embodiment at least about 1.05 moles ofnitrosylsulfuric acid per every one mole of aniline moiety in thepolyanthranilate, and in one embodiment no more than about 1.5 moles ofnitrosylsulfuric acid per every one mole of aniline moiety in thepolyanthranilate, in another embodiment no more than about 1.25 moles ofnitrosylsulfuric acid per every one mole of aniline moiety in thepolyanthranilate, and in yet another embodiment no more than about 1.15moles of nitrosylsulfuric acid per every one mole of aniline moiety inthe polyanthranilate, although the relative amounts can be outside ofthese ranges. In a specific embodiment, the nitrosylsulfuric acid isadded dropwise at a rate such that the temperature of the reactionmixture does not exceed 15° C.

The reaction to form the diazonium salt is essentially instantaneous,and upon completion of addition of the nitrosylsulfuric acid thereaction is essentially complete, although, if desired, a qualitativetest can be performed to confirm reaction completion.

Thereafter, residual excess nitrosylsulfuric acid present in thereaction mixture can be quenched by the addition of a quenching agent,such as sulfamic acid, urea, or the like as well as mixtures thereof, inany desired or effective amount, in one embodiment at least about 0.01mole of quenching agent per mole of nitrosylsulfuric acid (i.e., permole of nitrosylsulfuric acid originally added to the reaction mixture),in another embodiment at least about 0.05 mole of quenching agent permole of nitrosylsulfuric acid, and in yet another embodiment at leastabout 0.1 mole of quenching agent per mole of nitrosylsulfuric acid, andin one embodiment no more than about 0.5 mole of quenching agent permole of nitrosylsulfuric acid, in another embodiment no more than about0.3 mole of quenching agent per mole of nitrosylsulfuric acid, and inyet another embodiment no more than about 0.2 mole of quenching agentper mole of nitrosylsulfuric acid, although the amount can be outside ofthese ranges. Upon completion of the reaction, the reaction mixturecontains the corresponding diazonium salt.

A precursor solution of the pyridone having the desired substituentsthereon is prepared in an appropriate solvent, such as a mixture ofwater, organic solvents, including lower alcohols such as methanol,ethanol, isopropanol, and the like, water-miscible nonbasic organicsolvents such as tetrahydrofuran, acetone, dimethoxyethane,N,N-dimethylformamide, N,N-dimethylacetamide, and the like, as well asmixtures thereof. Mixtures of water with an organic solvent can behelpful for ease of solvating inorganic or organic salts that are areaction by-product. In this instance, water and the organic solvent arepresent in any desired or effective relative amounts, in one embodimentat least about 0.25 gram of organic solvent per gram of water, inanother embodiment at least about 0.3 gram of organic solvent per gramof water, and in yet another embodiment at least about 0.4 gram oforganic solvent per gram of water, and in one embodiment no more thanabout 4 grams of organic solvent per gram of water, in anotherembodiment no more than about 3 grams of organic solvent per gram ofwater, and in yet another embodiment no more than about 2 grams oforganic solvent per gram of water, although the relative amounts can beoutside of these ranges.

The pyridone is present in the precursor solution in any desired oreffective amount, in one embodiment at least about 10 grams of pyridoneper liter of solvent, in another embodiment at least about 30 grams ofpyridone per liter of solvent, and in yet another embodiment at leastabout 50 grams of pyridone per liter of solvent, and in one embodimentno more than about 200 grams of pyridone per liter of solvent, inanother embodiment no more than about 100 grams of pyridone per liter ofsolvent, and in yet another embodiment no more than about 70 grams ofpyridone per liter of solvent, although the relative amounts can beoutside of these ranges.

The pyridone precursor solution is maintained at an alkaline pH,typically of at least about 10, and in one embodiment no more than about14, and in another embodiment no more than about 12, although the pH canbe outside of these ranges. The pyridone precursor solution can containa mixture of a base and an optional buffering salt.

Examples of suitable bases include mineral bases, such as sodiumhydroxide, potassium hydroxide, and the like, as well as water-miscibleorganic tertiary amines, such as triethanolamine,N,N-diethylethanolamine, and the like, as well as mixtures thereof,present in any desired or effective amount, in one embodiment at leastabout 1 mole of base per mole of pyridone, in another embodiment atleast about 2 moles of base per mole of pyridone, in yet anotherembodiment at least about 3 moles of base per mole of pyridone, and instill another embodiment at least about 5 moles of base per mole ofpyridone, and in one embodiment no more than about 10 moles of base permole of pyridone, in another embodiment no more than about 7 moles ofbase per mole of pyridone, and in yet another embodiment no more thanabout 5 moles of base per mole of pyridone, although the relativeamounts can be outside of these ranges.

Examples of suitable optional buffer salts include those correspondingto the principal acid solvent; for example, when the principal acidsolvent is acetic acid, suitable buffers include sodium acetate,potassium acetate, sodium hydrogen phosphate, citric acid, and the like,as well as mixtures thereof. When present, the optional buffer salt ispresent in any desired or effective amount, in one embodiment at leastabout 1 mole of buffer per mole of pyridone, in another embodiment atleast about 2 moles of buffer per mole of pyridone, in yet anotherembodiment at least about 3 moles of buffer per mole of pyridone, and instill another embodiment at least about 5 moles of buffer per mole ofpyridone, and in one embodiment no more than about 10 moles of bufferper mole of pyridone, in another embodiment no more than about 7 molesof buffer per mole of pyridone, and in yet another embodiment no morethan about 5 moles of buffer per mole of pyridone, although the relativeamounts can be outside of these ranges. In a specific embodiment, upondissolution of the pyridone, the thus-formed precursor pyridone solutioncan be filtered to remove any undissolved solids.

The solution containing the diazonium salt, maintained at a coldtemperature, is then slowly added to the pyridone solution in anydesired or effective relative amounts, in one embodiment at least about1 mole of pyridone per mole of diazonium salt, in another embodiment atleast about 1.2 moles of pyridone per mole of diazonium salt, and in yetanother embodiment at least about 1.5 moles of pyridone per mole ofdiazonium salt, and in one embodiment no more than about 3 moles ofpyridone per mole of diazonium salt, in another embodiment no more thanabout 2 moles of pyridone per mole of diazonium salt, and in yet anotherembodiment no more than about 1.6 moles of pyridone per mole ofdiazonium salt, although the relative amounts can be outside of theseranges, resulting in the immediate formation of a bright yellowprecipitate. Thereafter, the yellow precipitate can be collected byfiltration and, if desired, washed.

Precursor polyanilines can be prepared by any desired or effectivemethod, such as that disclosed in, for example, “The Chemistry ofIsatoic Anhydride,” G. M. Coppola, Synthesis, p. 505 (1980); “IsatoicAnhydride. IV. Reactions with Various Nucleophiles,” R. P. Staiger etal., J. Org. Chem., Vol. 24, p. 1214 (1959); R. P. Staiger et al., J.Chem. Eng. Data B, p. 454 (1963); and U.S. Pat. No. 4,016,143; thedisclosures of each of which are totally incorporated herein byreference.

In addition, precursor polyanthranilates can be prepared by admixing (1)the correspondingly substituted triol or higher alcohol having thedesired structure wherein the hydroxy groups are primary or secondary,with (2) isatoic anhydride, (3) a base catalyst, and (4) a solvent; and(b) heating the mixture thus formed to form the desired polyanthranilateprecursor compound.

Isatoic anhydride and the selected polyol are present in any desired oreffective relative amounts, in one embodiment at least about 1 mole ofisatoic anhydride per every one mole of hydroxy groups present in thepolyol, in another embodiment at least about 1.02 moles of isatoicanhydride per every one mole of hydroxy groups present in the polyol, inyet another embodiment at least about 1.05 moles of isatoic anhydrideper every one mole of hydroxy groups present in the polyol, and in stillanother embodiment at least about 1.1 moles of isatoic anhydride perevery one mole of hydroxy groups present in the polyol, and in oneembodiment no more than about 2.5 moles of isatoic anhydride per everyone mole of hydroxy groups present in the polyol, in another embodimentno more than about 1.5 moles of isatoic anhydride per every one mole ofhydroxy groups present in the polyol, and in yet another embodiment nomore than about 1.2 moles of isatoic anhydride per every one mole ofhydroxy groups present in the polyol, although the relative amounts ofreactants can be outside of these ranges.

Examples of suitable catalysts include 1,4-diazabicyclo(2.2.2) octane,N,N,N′,N′-tetramethylethylene diamine, mixtures thereof, and the like.The catalyst is present in the reaction mixture in any desired oreffective amount, in one embodiment at least about 0.1 mole of catalystper every one mole of hydroxy groups present in the polyol, in anotherembodiment at least about 0.11 mole of catalyst per every one mole ofhydroxy groups present in the polyol, in yet another embodiment at leastabout 0.12 mmole of catalyst per every one mole of hydroxy groupspresent in the polyol, and in still another embodiment at least about0.25 mole of catalyst per every one mole of hydroxy groups present inthe polyol, and in one embodiment no more than about 1 mole of catalystper every one mole of hydroxy groups present in the polyol, in anotherembodiment no more than about 0.5 mole of catalyst per every one mole ofhydroxy groups present in the polyol, and in yet another embodiment nomore than about 0.26 mole of catalyst per every one mole of hydroxygroups present in the polyol, although the relative amount of catalystcan be outside of these ranges.

The reactants typically are present in a suitable solvent. The reactantscan be either soluble or insoluble in the solvent, resulting in ahomogeneous or a heterogeneous reaction mixture. Examples of suitablesolvents include toluene, xylene, methyl ethyl ketone, ethyl acetate,butyl acetate, chlorobenzene, dioxane, dimethylformamide,N-methyl-2-pyrrolidinone, dimethylsulfoxide, sulfolane, pyridone, andthe like, as well as mixtures thereof, with toluene and butyl acetatebeing preferred.

The reactants can be present in the solvent in any desired or effectiverelative amounts. The solvent is present in an amount of in oneembodiment at least about 0.1 mole of polyol per liter of solvent, inanother embodiment at least about 0.25 mole of polyol per liter ofsolvent, in yet another embodiment at least about 0.5 mole of polyol perliter of solvent, and in still another embodiment at least about 0.75mole of polyol per liter of solvent, and is present in an amount of inone embodiment no more than about 3 moles of polyol per liter ofsolvent, in another embodiment no more than about 2 moles of polyol perliter of solvent, in yet another embodiment no more than about 1.5 molesof polyol per liter of solvent, and in still another embodiment no morethan about 0.75 mole of polyol per liter of solvent, although therelative amount of solvent can be outside of these ranges.

The reaction mixture is heated to any desired or effective temperature,in one embodiment to a temperature of at least about 40° C., in anotherembodiment to a temperature of at least about 75° C., and in yet anotherembodiment to a temperature of at least about 100° C., and is heated inone embodiment to a temperature of no more than about 200° C., inanother embodiment to a temperature of no more than about 170° C., andin yet another embodiment of no more than about 150° C., although thetemperature can be outside of these ranges.

The reaction is carried out by heating for any desired or effectiveamount of time, in one embodiment for a period of at least about 1 hour,in another embodiment for a period of at least about 2.5 hours, and inyet another embodiment for a period of at least about 3 hours, and inone embodiment for a period of no more than about 10 hours, in anotherembodiment for a period of no more than about 6 hours, and in yetanother embodiment for a period of no more than about 3.5 hours,although the reaction time can be outside of these ranges.

Subsequent to completion of the reaction, excess isatoic anhydride canbe quenched, by, for example, the dropwise addition of a dilute solution(about 5 percent, for example) of aqueous sodium or potassium hydroxideto convert isatoic anhydride to the water-soluble sodium or potassiumsalt of anthranilic acid. Alternately, excess isatoic anhydride can bereacted with methanol or ethanol, which converts it to methyl or ethylanthranilate, both of which are liquids soluble in common organicsolvents, such as alcohols, ethers, ketones, esters, and the like.

The polyanthranilate product can be separated from the reaction mixtureby any desired or effective method. For example, liquid-liquidextraction, which may be desirable when the polyanthranilate is notcrystalline at ambient temperature, can be carried out between theorganic phase and the aqueous phase of the mixture. (Said aqueous phasecan be added when the reaction mixture is subjected to quenching with anaqueous solution; when such quenching is not carried out, water can beadded to create the aqueous phase.) In the event of formation of anemulsion between these phases, which could make separation of the layersdifficult or very slow, techniques known to those skilled in the art ofextractive separation, such as, for example, adding more of the same ora different organic solvent to the organic layer, such as ethyl acetateor the like, and/or adding a salt, such as, for example, sodiumchloride, potassium chloride, ammonium sulfate, or the like (typicallyin amounts from about 5 to about 30 percent by weight in water) can beperformed. The organic phase can then, if desired, be dried by anydesired or effective method, such as by drying over magnesium sulfate,or the like. The product can then be isolated by removal of the solventby any desired or effective method, such as vacuum distillation or thelike. If desired, the resulting product, while it is still dissolved inthe organic phase, can be treated with acidic media, such as anacid-leached bentonite clay (available from Englehart Industries underthe Trade name FILTROL® 24), which treatment can serve to remove anyundesirable colored basic impurities.

The polyanthranilate product can also be separated from the reactionmixture by precipitation using a non-solvent, which may be desirablewhen the polyanthranilate product is crystalline. In this situation, alow alcohol, such as methanol or ethanol, is added to the reactionmixture in a molar amount greater than or equal to the amount ofunreacted isatoic anhydride, either after cooling to room temperature orat a temperature of up to about 80° C., which serves to convert excessisatoic anhydride to the liquid methyl or ethyl anthranilate. Additionof a non-solvent for the polyanthranilate, such as water, methanol,isopropanol, or the like is then used to precipitate the product, whichcan then be separated by filtration, washing with a suitable solvent,and drying.

Precursor pyridones can be prepared by any desired or effective method,such as that disclosed in, for example, “Investigation of the ReactionConditions for the Synthesis of 4,6-Disubstituted-3-cyano-2-pyridonesand 4-Methyl-3-cyano-6-hydroxy-2-pyridone,” D. Z. Mijin et al., J. Serb.Chem. Soc., Vol. 59, No. 12, p. 959 (1994); “Synthesis of IsoquinolineAlkaloids. II. The Synthesis and Reactions of4-Methyl-3-pyridinecarboxaldehyde and Other 4-Methyl-3-substitutedPyridines,” J. M. Bobbitt et al., J. Org. Chem., Vol. 25, p. 560 (1960);“Synthesis and Dyeing Characteristics of5-(4-Arylazophenyl)azo-3-cyano-4-methyl-6-hydroxy-2-pyridones,” J. M.Kanhere et al., Indian Journal of Textile Research, Vol. 13, p. 213(1988); “Synthesis of Some Pyridone Azo Dyes from 1-Substituted2-Hydroxy-6-pyridone Derivatives and their Colour Assessment,” C. Chenet al., Dyes and Pigments, Vol. 15, p. 69 (1991); “Synthesis of3-Cyano-6-hydroxy-5-(2-(perfluoroalkyl)phenylazo)-2-pyridones and theirApplication for Dye Diffusion Thermal Transfer Printing,” M. Matsui etal., Bull. Chem. Soc. Jpn., 1993, Vol. 66, Iss. 6, Pp. 1790-4;“Synthesis of N-alkylcyanopyridones,” B. Peng et al., Faming ZhuanliShenqing Gongkai Shuomingshu (1997), CN 1158845; “Synthesis of1-Butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one,” X. Kong et al., HuaxueShiji (1998), 20(1), 58-59; “Regioselective Conversion of3-Cyano-6-hydroxy-2-pyridones into 3-Cyano-6-amino-2-pyridones,” A. R.Katritzky et al., J. Heterocycl. Chem. (1995), 32(3), 1007-10; “TheSynthesis of Some Hetarylazopyridone Dyes and Solvent Effects on theirAbsorption Spectra,” N. Ertan et al., Dyes Pigm. (1995), 27(4), 313-20;“Process for the Preparation of Pyridone Compounds,” H. Schmid, Ger.Offen. DE 4314430 (1994); “Tautomerism of 4-Methyl-6-hydroxy-2-pyridonederivatives,” H. Liu et al., Dalian Ligong Daxue Xueboo (1992), 32(4),405-11; “Preparation of1-Alkyl-3-cyano-4-methyl-6-hydroxy-2-pyridone-type Mixed Azo CouplingComponents,” J. Prikryl et al., Czech. (1991) 8 pp. CODEN: CZXXA9 CS273045 Bl 19911220 CAN 118:256604 AN 1993:256604 CAPLUS; “StructuralCharacteristics of Hydroxypyridone Derivatives,” Q. Peng et al., DalianLigong Daxue Xuebao (1991), 31(3), 279-86; and“6-Hydroxypyridin-2-ones,” F. Schmidt, Ger. Offen. DE 2845863 (1980);the disclosures of each of which are totally incorporated herein byreference.

When polymeric products are desired, polymers having three or morependant primary or secondary alcohol or hydroxy groups, in oneembodiment at least about 6 alcohol or hydroxy groups, and in anotherembodiment at least about 10 alcohol or hydroxy groups, and in oneembodiment no more than about 30 alcohol or hydroxy groups, and inanother embodiment no more than about 20 alcohol or hydroxy groups,although the number of alcohol or hydroxy groups can be outside of theseranges, can be converted to polyanthranilates by the method describedhereinabove. Any desired or effective polymer can be employed, such aspolyvinyl alcohol, commercially available, polyvinyl acetate which hasbeen reduced, or the like.

Colorants wherein the

moieties are linked to the central atom or group of atoms or bonded to apolymer through R₂ can be prepared by any desired or effective method.For example, they can be prepared by formation of pyridone moieties onthe central atom or group of atoms or oligomer or polymer. Pyridonemoieties can be formed by, for example, converting primary amino groupsto pyridone moieties by reactions with esters as described in furtherdetail hereinbelow. The pyridone moieties can in turn be coupled in abuffered alkaline aqueous solution under cold temperature conditionswith a stoichiometric number of anthranilate moieties which have beenpreviously diazotized with nitrosylsulfuric acid under cold temperatureconditions. More specifically, the anthranilate is first subjected to adiazotization reaction by dissolving it in acetic acid diluted with asolvent and, optionally, a second acid, such as sulfuric acid,dodecylbenzene sulfonic acid, propionic acid, hydrochloric acid,phosphoric acid, any other acid useful for a diazotization reaction, orthe like, as well as mixtures thereof. The solvent can be any solventuseful in a diazotization reaction, such as water, acetone,dimethylformamide, dimethyacetamide, tetrahydrofuran, dimethoxyethane,analogous higher-boiling ether solvents, and the like, as well asmixtures thereof.

The solvent and the anthranilate are present in any desired or effectiverelative amounts; if, for purposes of determining relative amounts,“solvent” is defined to include whatever solvent has been selected plusany amount of acetic acid and second acid present, the reactants arepresent in this combined solvent in relative amounts of in oneembodiment at least about 100 grams of anthranilate per liter ofsolvent, in another embodiment at least about 200 grams of anthranilateper liter of solvent, and in yet another embodiment at least about 230grams of anthranilate per liter of solvent, and in one embodiment of nomore than about 400 grams of anthranilate per liter of solvent, inanother embodiment of no more than about 300 grams of anthranilate perliter of solvent, and in yet another embodiment of no more than about270 grams of anthranilate per liter of solvent, although the relativeamounts can be outside of these ranges.

The acetic acid is present in any desired or effective amount, in oneembodiment at least about 1 gram of acetic acid per gram ofanthranilate, in another embodiment at least about 2 grams of aceticacid per gram of anthranilate, and in yet another embodiment at leastabout 3 grams of acetic acid per gram of anthranilate, and in oneembodiment no more than about 10 grams of acetic acid per gram ofanthranilate, in another embodiment no more than about 7 grams of aceticacid per gram of anthranilate, and in yet another embodiment no morethan about 5 grams of acetic acid per gram of anthranilate, although therelative amounts can be outside of these ranges.

When present, the optional second acid is present in any desired oreffective amount, in one embodiment at least about 0.05 gram of acid pergram of anthranilate, and in another embodiment at least about 0.1 gramof acid per gram of anthranilate, and in one embodiment no more thanabout 0.5 grams of acid per gram of anthranilate, in another embodimentno more than about 0.3 grams of acid per gram of anthranilate, and inyet another embodiment no more than about 0.2 grams of acid per gram ofanthranilate, although the relative amounts can be outside of theseranges.

In the mixture comprising the selected solvent, any optional secondacid, and acetic acid, the acetic acid is present in any desired oreffective amount, in one embodiment at least about 50 percent by volumeof the mixture, in another embodiment at least about 70 percent byvolume of the mixture, in yet another embodiment at least about 75percent by volume of the mixture, and in still another embodiment atleast about 95 percent by volume of the mixture, although the relativeamount can be outside of these ranges.

Upon complete dissolution of the ingredients, the mixture is cooled, inone embodiment to a temperature of no more than about +15° C., inanother embodiment to a temperature of no more than about +10° C., inyet another embodiment to a temperature of no more than about +5° C., instill another embodiment to a temperature of no more than about +3° C.,and in one embodiment to a temperature of no lower than about −5° C.,and in another embodiment to a temperature of no lower than about −10°C., although the temperature can be outside of these ranges.

Thereafter, nitrosylsulfuric acid is added to the mixture in any desiredor effective amount, in one embodiment at least about 1 mole ofnitrosylsulfuric acid per mole of anthranilate, and in anotherembodiment at least about 1.05 moles of nitrosylsulfuric acid per moleof anthranilate, and in one embodiment no more than about 1.5 moles ofnitrosylsulfuric acid per mole of anthranilate, in another embodiment nomore than about 1.25 moles of nitrosylsulfuric acid per mole ofanthranilate, and in yet another embodiment no more than about 1.15moles of nitrosylsulfuric acid per mole of anthranilate, although therelative amounts can be outside of these ranges. In a specificembodiment, the nitrosylsulfuric acid is added dropwise at a rate suchthat the temperature of the reaction mixture does not exceed 15° C.

The reaction is essentially instantaneous, and upon completion ofaddition of the nitrosylsulfuric acid the reaction is essentiallycomplete, although, if desired, a qualitative test can be performed toconfirm reaction completion.

Thereafter, residual excess nitrosylsulfuric acid present in thereaction mixture can be quenched by the addition of a quenching agent,such as sulfamic acid, urea, or the like as well as mixtures thereof, inany desired or effective amount, in one embodiment at least about 0.01mole of quenching agent per mole of nitrosylsulfuric acid (i.e., permole of nitrosylsulfuric acid originally added to the reaction mixture),in another embodiment at least about 0.05 mole of quenching agent permole of nitrosylsulfuric acid, and in yet another embodiment at leastabout 0.1 mole of quenching agent per mole of nitrosylsulfuric acid, andin one embodiment no more than about 0.5 mole of quenching agent permole of nitrosylsulfuric acid, in another embodiment no more than about0.3 mole of quenching agent per mole of nitrosylsulfuric acid, and inyet another embodiment no more than about 0.2 mole of quenching agentper mole of nitrosylsulfuric acid, although the amount can be outside ofthese ranges. Upon completion of the reaction, the reaction mixturecontains the corresponding diazonium salt.

A precursor solution of the tripyridone, tetrapyridone, pentapyridone,hexapyridone, or otherwise desirably substituted pyridone having thedesired structure (hereinafter referred to as the “polypyridone”; thisterm includes monomeric tripyridones, tetrapyridones, pentapyridones,hexapyridones, and the like, oligomeric pyridones, and polymericpyridones) is prepared in an appropriate solvent, such as a mixture ofwater, organic solvents, including lower alcohols such as methanol,ethanol, isopropanol, and the like, water-miscible nonbasic organicsolvents such as tetrahydrofuran, acetone, dimethoxyethane,N,N-dimethylformamide, N,N-dimethylacetamide, and the like, as well asmixtures thereof. Mixtures of water with an organic solvent can behelpful for ease of solvating inorganic and organic salts that are areaction by-product. In this instance, water and the organic solvent arepresent in any desired or effective relative amounts, in one embodimentat least about 0.25 gram of organic solvent per gram of water, inanother embodiment at least about 0.3 gram of organic solvent per gramof water, and in yet another embodiment at least about 0.4 gram oforganic solvent per gram of water, and in one embodiment no more thanabout 4 grams of organic solvent per gram of water, in anotherembodiment no more than about 3 grams of organic solvent per gram ofwater, and in yet another embodiment no more than about 2 grams oforganic solvent per gram of water, although the relative amounts can beoutside of these ranges.

The polypyridone is present in the precursor solution in any desired oreffective amount, in one embodiment at least about 10 grams ofpolypyridone per liter of solvent, in another embodiment at least about30 grams of polypyridone per liter of solvent, and in yet anotherembodiment at least about 50 grams of polypyridone per liter of solvent,and in one embodiment no more than about 200 grams of polypyridone perliter of solvent, in another embodiment no more than about 100 grams ofpolypyridone per liter of solvent, and in yet another embodiment no morethan about 70 grams of polypyridone-per liter of solvent, although therelative amounts can be outside of these ranges.

The polypyridone precursor solution is maintained at an alkaline pH,typically of at least about 10, and in one embodiment no more than about14, and in another embodiment no more than about 12, although the pH canbe outside of these ranges. The polypyridone precursor solution cancontain a mixture of a base and an optional buffering salt.

Examples of suitable bases include mineral bases, such as sodiumhydroxide, potassium hydroxide, and the like, as well as water-miscibleorganic tertiary amines, such as triethanolamine,N,N-diethylethanolamine, and the like, as well as mixtures thereof,present in any desired or effective amount, in one embodiment at leastabout 1 mole of base per every one mole of pyridone moiety in thepolypyridone, in another embodiment at least about 2 moles of base perevery one mole of pyridone moiety in the polypyridone, in yet anotherembodiment at least about 3 moles of base per mole of dipyridone, and instill another embodiment at least about 5 moles of base per every onemole of pyridone moiety in the polypyridone, and in one embodiment nomore than about 10 moles of base per every one mole of pyridone moietyin the polypyridone, in another embodiment no more than about 7 moles ofbase per every one mole of pyridone moiety in the polypyridone, and inyet another embodiment no more than about 5 moles of base per every onemole of pyridone moiety in the polypyridone, although the relativeamounts can be outside of these ranges.

Examples of suitable buffer salts include those corresponding to theprincipal acid solvent; for example, when the principal acid solvent isacetic acid, suitable buffers include sodium acetate, potassium acetate,sodium hydrogenphosphate, citric acid, and the like, as well as mixturesthereof, present in any desired or effective amount, in one embodimentat least about 1 mole of buffer per every one mole of pyridone moietiesin the polypyridone, in another embodiment at least about 2 moles ofbuffer per every one mole of pyridone moieties in the polypyridone, inyet another embodiment at least about 3 moles of buffer per every onemole of pyridone moieties in the polypyridone, and in still anotherembodiment at least about 5 moles of buffer per every one mole ofpyridone moieties in the polypyridone, and in one embodiment no morethan about 10 moles of buffer per every one mole of pyridone moieties inthe polypyridone, in another embodiment no more than about 7 moles ofbuffer per every one mole of pyridone moieties in the polypyridone, andin yet another embodiment no more than about 5 moles of buffer per everyone mole of pyridone moieties in the polypyridone, although the relativeamounts can be outside of these ranges. In a specific embodiment, upondissolution of the dipyridone, the thus-formed precursor polypyridonesolution can be filtered to remove any undissolved solids.

The solution containing the diazonium salt, maintained at a coldtemperature, is then slowly added to the polypyridone solution in anydesired or effective relative amounts, in one embodiment at least about1 mole of pyridone moiety per mole of diazonium salt, in anotherembodiment at least about 1.2 moles of pyridone moieties per mole ofdiazonium salt, and in yet another embodiment at least about 1.5 molesof pyridone moieties per mole of diazonium salt, and in one embodimentno more than about 3 moles of pyridone moieties per mole of diazoniumsalt, in another embodiment no more than about 2 moles of pyridonemoieties per mole of diazonium salt, and in yet another embodiment nomore than about 1.6 moles of pyridone moieties per mole of diazoniumsalt, although the relative amounts can be outside of these ranges,resulting in the immediate formation of a bright yellow precipitate.Thereafter, the yellow precipitate can be collected by filtration and,if desired, washed.

Precursor anthranilates can be prepared by any desired or effectivemethod, such as that disclosed in, for example, “The Chemistry ofIsatoic Anhydride,” G. M. Coppola, Synthesis, p. 505 (1980); “IsatoicAnhydride. IV. Reactions with Various Nucleophiles,” R. P. Staiger etal., J. Org. Chem., Vol. 24, p. 1214 (1959); R. P. Staiger et al., J.Chem. Eng. Data B, p. 454 (1963); and U.S. Pat. No. 4,016,143; thedisclosures of each of which are totally incorporated herein byreference.

Precursor polypyridones can be prepared by any desired or effectivemethod, such as that disclosed in, for example, “Investigation of theReaction Conditions for the Synthesis of4,6-Disubstituted-3-cyano-2-pyridones and4-Methyl-3-cyano-6-hydroxy-2-pyridone,” D. Z. Mijin et al., J. Serb.Chem. Soc., Vol. 59, No. 12, p. 959 (1994); “Synthesis of IsoquinolineAlkaloids. II. The Synthesis and Reactions of4-Methyl-3-pyridinecarboxaldehyde and Other 4-Methyl-3-substitutedPyridines,” J. M. Bobbitt et al., J. Org. Chem., Vol. 25, p. 560 (1960);“Synthesis and Dyeing Characteristics of5-(4-Arylazophenyl)azo-3-cyano-4-methyl-6-hydroxy-2-pyridones,” J. M.Kanhere et al., Indian Journal of Textile Research, Vol. 13, p. 213(1988); “Synthesis of Some Pyridone Azo Dyes from 1-Substituted2-Hydroxy-6-pyridone Derivatives and their Colour Assessment,” C. Chenet al., Dyes and Pigments, Vol. 15, p. 69 (1991); “Synthesis of3-Cyano-6-hydroxy-5-(2-(perfluoroalkyl)phenylazo)-2-pyridones and theirApplication for Dye Diffusion Thermal Transfer Printing,” M. Matsui etal., Bull. Chem. Soc. Jpn., 1993, Vol. 66, Iss. 6, Pp. 1790-4;“Synthesis of N-alkylcyanopyridones,” B. Peng et al., Faming ZhuanliShenqing Gongkai Shuomingshu (1997), CN 1158845; “Synthesis of1-Butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one,” X. Kong et al., HuaxueShiji (1998), 20(1), 58-59; “Regioselective Conversion of3-Cyano-6-hydroxy-2-pyridones into 3-Cyano-6-amino-2-pyridones,” A. R.Katritzky et al., J. Heterocycl. Chem. (1995), 32(3), 1007-10; “TheSynthesis of Some Hetarylazopyridone Dyes and Solvent Effects on theirAbsorption Spectra,” N. Ertan et al., Dyes Pigm. (1995), 27(4), 313-20;“Process for the Preparation of Pyridone Compounds,” H. Schmid, Ger.Offen. DE 4314430 (1994); “Tautomerism of 4-Methyl-6-hydroxy-2-pyridonederivatives,” H. Liu et al., Dalian Ligong Daxue Xueboo (1992), 32(4),405-11; “Preparation of1-Alkyl-3-cyano-4-methyl-6-hydroxy-2-pyridone-type Mixed Azo CouplingComponents,” J. Prikryl et al., Czech. (1991) 8 pp. CODEN: CZXXA9 CS273045 Bl 19911220 CAN 118:256604 AN 1993:256604 CAPLUS; “StructuralCharacteristics of Hydroxypyridone Derivatives,” Q. Peng et al., DalianLigong Daxue Xueboo (1991), 31(3), 279-86; and“6-Hydroxypyridin-2-ones,” F. Schmidt, Ger. Offen. DE 2845863 (1980);the disclosures of each of which are totally incorporated herein byreference.

In addition, precursor polypyridones can be prepared by first preparinga corresponding intermediate compound by reacting a polyamine with afirst ester compound, as follows:

wherein R₂ is as defined hereinabove, n is an integer of three orgreater, and R_(x) is an alkyl group (including linear, branched,saturated, unsaturated, cyclic, unsubstituted, and substituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inone embodiment with no more than about 5 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl,1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl,1,3-dimethyl propyl, and the like. For example, some examples oftriamines that can be used in this reaction include (but are not limitedto) tris(2-aminoethyl)amine, of the formula

3-methyleneoctane-1,8-diyl triamine, of the formula

and the like, as well as mixtures thereof. Examples of suitable firstester compounds include methyl cyanoacetate, ethyl cyanoacetate,n-propyl cyanoacetate, isopropyl cyanoacetate, n-butyl cyanoacetate,tert-butyl cyanoacetate, and the like, as well as mixtures thereof. Thisreaction can, if desired, take place in the absence of any solvent.

The polyamine and the first ester are present in any desired oreffective relative amounts, in one embodiment at least about 0.75 moleof amine moiety per every one mole of ester moiety (i.e., in theinstance of a triamine, 0.25 mole of triamine molecule per every mole ofester molecule), in another embodiment at least about 0.9 mole of aminemoiety per every one mole of ester moiety, and in yet another embodimentat least about 0.95 mole of amine moiety per every one mole of estermoiety, and in one embodiment no more than about 1.25 moles of aminemoiety per every one mole of ester moiety, in another embodiment no morethan about 1.1 moles of amine moiety per every one mole of ester moiety,and in yet another embodiment no more than about 1.0 mole of aminemoiety per every one mole of ester moiety, although the relative amountsof reactants can be outside of these ranges.

The mixture of the polyamine and the first ester is heated to anydesired or effective temperature to effect the conversion to theintermediate compound, in one embodiment to a temperature of at leastabout 80° C., in another embodiment to a temperature of at least about100° C., and in yet another embodiment to a temperature of at leastabout 110° C., and is heated in one embodiment to a temperature of nomore than about 160° C., in another embodiment to a temperature of nomore than about 140° C., and in yet another embodiment of no more thanabout 120° C., although the temperature can be outside of these ranges.

The reaction between the polyamine and the first ester is carried out byheating for any desired or effective amount of time, in one embodimentfor a period of at least about 10 minutes, in another embodiment for aperiod of at least about 30 minutes, and in yet another embodiment for aperiod of at least about 45 minutes, and in one embodiment for a periodof no more than about 480 minutes, in another embodiment for a period ofno more than about 240 minutes, and in yet another embodiment for aperiod of no more than about 120 minutes, although the reaction time canbe outside of these ranges.

The intermediate compound thus formed is then reacted with a secondester and a base (“B”) to form the desired pyridone or a salt thereof,as follows:

If a salt is formed, it can later be converted to the hydroxy compoundby acidification, as follows:

In the second ester, R₃ is as defined hereinabove and R_(y) is an alkylgroup (including linear, branched, saturated, unsaturated, cyclic,unsubstituted, and substituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), in one embodimentwith at least 1 carbon atom, and in one embodiment with no more thanabout 5 carbon atoms, although the number of carbon atoms can be outsideof this range, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, t-butyl, pentyl, 1-methyl butyl, 2-methyl butyl, 3-methylbutyl, 2,2-dimethyl propyl, 1,3-dimethyl propyl, and the like. Specificexamples of second esters include methyl acetoacetate, ethylacetoacetate, t-butyl acetoacetate, ethyl butyrylacetate, and the like,as well as mixtures thereof.

Examples of suitable bases include piperidine, 1-methyl piperidine,1-ethylpiperidine, piperazine, 1-ethylpiperazine, 2-ethylpiperazine,1-methylpiperazine, 2-methylpiperazine, sodium hydroxide, triethylamine,tributylamine, dimethylethanolamine, diethylethanolamine,1,4-diazabicyclo(2.2.2)octane, morpholine, 4-ethylmorpholine,t-octylamine, hexamethyl disilazane, tetramethyl ethylenediamine,diethylcyclohexylamine, di-isopropylethylamine,4,4′-trimethylene-dipiperidine, 1,4-dimethyl-piperazine, benzimidazole,benzoxazole, dipiperidino-methane,tris-(2-(2-methoxyethoxy)-ethyl)amine, and the like, as well as mixturesthereof.

The intermediate compound and the second ester are present in relativeamounts such that the second ester is present in a molar excess, i.e.,the molar ratio of second ester to amide moiety in the intermediate isgreater than 1:1. The relative amounts of second ester and amide moietyin the intermediate are in one embodiment at least about 1.1 moles ofsecond ester per every one mole of amide moiety in the intermediate, inanother embodiment at least about 1.2 moles of second ester per everyone mole of amide moiety in the intermediate, in yet another embodimentat least about 1.5 moles of second ester per every one mole of amidemoiety in the intermediate, and in still another embodiment at leastabout 2 moles of second ester per every one mole of amide moiety in theintermediate, and in one embodiment no more than about 8 moles of secondester per every one mole of amide moiety in the intermediate, in anotherembodiment no more than about 4 moles of second ester per every one moleof amide moiety in the intermediate, and in yet another embodiment nomore than about 2 moles of second ester per every one mole of amidemoiety in the intermediate, although the relative amounts of reactantscan be outside of these ranges.

The intermediate compound and the base are present in relative amountssuch that the base is present in a molar excess, i.e., the molar ratioof base to amide moiety in the intermediate is greater than 1:1. Therelative amounts of base and amide moiety in the intermediate are in oneembodiment at least about 1.1 moles of base per every one mole of amidemoiety in the intermediate, in another embodiment at least about 1.2moles of base per every one mole of amide moiety in the intermediate, inyet another embodiment at least about 1.5 moles of base per every onemole of amide moiety in the intermediate, and in still anotherembodiment at least about 2 moles of base per every one mole of amidemoiety in the intermediate, and in one embodiment no more than about 8moles of base per every one mole of amide moiety in the intermediate, inanother embodiment no more than about 4 moles of base per every one moleof amide moiety in the intermediate, and in yet another embodiment nomore than about 2 moles of base per every one mole of amide moiety inthe intermediate, although the relative amounts of reactants can beoutside of these ranges.

The reaction between the intermediate compound and the second ester cantake place in the absence of a solvent, or, if desired for reasons suchas lowering the viscosity of the product solution, ease of productrecovery, or improved control of the reaction temperature, a solvent canbe used. Any desired or suitable solvent can be used. Examples ofsuitable solvents include dimethyl formamide, N-methylpyrrolidinone,toluene, sulfolane, and the like, as well as mixtures thereof.

When present, the solvent is present in any desired or effective amount,in one embodiment at least about 1 mole of intermediate per liter ofsolvent, in another embodiment at least about 2 moles of intermediateper liter of solvent, and in yet another embodiment at least about 2.5moles of intermediate per liter of solvent, and is present in an amountof in one embodiment no more than about 10 moles of intermediate perliter of solvent, in another embodiment no more than about 5 moles ofintermediate per liter of solvent, and in yet another embodiment no morethan about 3.5 moles of intermediate per liter of solvent, although therelative amount of solvent can be outside of these ranges.

The mixture of the intermediate, the base, and the second ester isheated to any desired or effective temperature to effect the conversionto the polypyridone product, in one embodiment to a temperature of atleast about 80° C., in another embodiment to a temperature of at leastabout 100° C., and in yet another embodiment to a temperature of atleast about 110° C., and is heated in one embodiment to a temperature ofno more than about 160° C., in another embodiment to a temperature of nomore than about 140° C., and in yet another embodiment of no more thanabout 120° C., although the temperature can be outside of these ranges.

The reaction between the intermediate, the base, and the second ester iscarried out by heating for any desired or effective amount of time, inone embodiment for a period of at least about 30 minutes, in anotherembodiment for a period of at least about 60 minutes, and in yet anotherembodiment for a period of at least about 120 minutes, and in oneembodiment for a period of no more than about 1,440 minutes, in anotherembodiment for a period of no more than about 480 minutes, and in yetanother embodiment for a period of no more than about −240 minutes,although the reaction time can be outside of these ranges.

Subsequent to completion of the reaction, the polypyridone product canbe recovered by cooling the reaction mixture to room temperature andpouring it into a non-solvent for the polypyridone product. Examples ofsuitable non-solvents include water, methanol, ethanol, n-propanol,isopropanol, butanol, ethyl acetate, propyl acetate, butyl acetate, andthe like, as well as mixtures thereof. For example, mixtures containingfrom 50 to 80 parts by volume methanol and from 20 to 50 parts by volumewater, and more preferably containing from 60 to 80 parts by volumemethanol and from 20 to 40 parts by volume water, were found to beparticularly effective.

If desired, to convert any polypyridone salt product to the hydroxyform, the non-solvent into which the reaction mixture is poured can beacidified. Any desired or suitable acid can be employed, such ashydrochloric acid, nitric acid, sulfuric acid, and the like, as well asmixtures thereof. In this instance, the acid is present in any desiredor effective amount, in one embodiment at least about 1 mole of acid permole of base used in the synthesis process (including any unreactedpolyamine believed to be present from the reaction of the polyamine withthe first ester), in another embodiment at least about 1.2 moles of acidper mole of base used in the synthesis process, and in yet anotherembodiment at least about 1.3 moles of acid per mole of base used in thesynthesis process, and in one embodiment no more than about 3 moles ofacid per mole of base used in the synthesis process, in anotherembodiment no more than about 2 moles of acid per mole of base used inthe synthesis process, and in yet another embodiment no more than about1.5 moles of acid per mole of base used in the synthesis process,although the amount of acid can be outside of these ranges.

The precipitated product can then be collected by any desired method,such as filtration or the like, washed, and dried. For washing, amixture of 50 parts by weight methanol and 50 parts by weight water wasfound to be particularly effective.

When polymeric products are desired, polymers having three or morependant primary amino groups, in one embodiment at least about 6 aminogroups, and in another embodiment at least about 10 amino groups, and inone embodiment no more than about 30 amino groups, and in anotherembodiment no more than about 20 amino groups, although the number ofamino groups can be outside of these ranges, can be converted topolypyridones by the method described hereinabove. Any desired oreffective polymer can be employed, such as commercially availablepolymers having primary amino groups thereon, polyacrylonitrile whichhas been reduced, or the like.

While not being limited to any particular theory, it is believed thatthe ortho-substitution structural feature of the colorant moleculesenables the formation of strong intramolecular hydrogen bonds betweenthe azo group, the hydroxyl group, and the carbonyl group that impartsrigidity and significant photostability to the colorant under visiblelight conditions. It is believed that these bonds form as follows(showing here both the enol and the hydrazone tautomers in which thistype of molecule exists, as taught by, for example, “Synthesis of SomePyridone Azo Dyes from 1-Substituted 2-Hydroxy-6-pyridone Derivativesand their Colour Assessment,” C. Chen et al., Dyes and Pigments, Vol.15, p. 69 (1991), the disclosure of which is totally incorporated hereinby reference):

It is believed that this structural feature can also impart thermalstability and chemical stability to the colorant molecule. Further,while not being limited to any particular theory, it is believed thatthe high molecular weight of the colorant molecule further reducesdiffusion or leaching of the colorant molecule from a medium such as aphase change ink vehicle into adjacent inks of different colors (leadingto intercolor bleed), adjacent unprinted areas (leading to edgeraggedness), directly through the substrate (leading to show through)tape adhesives (leading to edge raggedness and possible illegibility),and the like. Additionally, it is believed that by including multipleazo pyridone chromophores within the colorant molecule, the spectralstrength of the colorant is substantially increased, enabling the use ofsubstantially reduced amounts of colorant in, for example, an inkwithout decreasing the color and the spectral properties (L*a*b*) of theink or jeopardizing the optical density or color of the prints generatedwith the ink.

In addition to being suitable for use in phase change inks, thecolorants of the present invention can be used in applications such astextile dying, biological dying applications that rely on high spectralstrength chromophores, electronics applications, such as organicphotoconductors, optical filters, and the like, color filters for liquidcrystal display systems, and the like.

Phase change inks as disclosed herein contain a phase change carriersystem or composition. The phase change carrier composition is typicallydesigned for use in either a direct printing mode or an indirect oroffset printing transfer system.

In the direct printing mode, the phase change carrier composition in oneembodiment contains one or more materials that enable the phase changeink (1) to be applied in a thin film of uniform thickness on the finalrecording substrate (such as paper, transparency material, and the like)when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

In an offset printing transfer or indirect printing mode, the phasechange carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference.

Any desired or effective carrier composition can be used. Examples ofsuitable ink carrier materials include fatty amides, such as monoamides,tetra-amides, mixtures thereof, and the like. Specific examples ofsuitable fatty amide ink carrier materials include stearyl stearamide, adimer acid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and stearic acid, a dimer acid based tetra-amide thatis the reaction product of dimer acid, ethylene diamine, and acarboxylic acid having at least about 36 carbon atoms, and the like, aswell as mixtures thereof. When the fatty amide ink carrier is a dimeracid based tetra-amide that is the reaction product of dimer acid,ethylene diamine, and a carboxylic acid having at least about 36 carbonatoms, the carboxylic acid is of the general formula

wherein R is an alkyl group, including linear, branched, saturated,unsaturated, and cyclic alkyl groups, said alkyl group in one embodimenthaving at least about 36 carbon atoms, in another embodiment having atleast about 40 carbon atoms, said alkyl group in one embodiment havingno more than about 200 carbon atoms, in another embodiment having nomore than about 150 carbon atoms, and in yet another embodiment havingno more than about 100 carbon atoms, although the number of carbon atomscan be outside of these ranges. Carboxylic acids of this formula arecommercially available from, for example, Baker Petrolite, Tulsa, Okla.,and can also be prepared as described in Example 1 of U.S. Pat. No.6,174,937, the disclosure of which is totally incorporated herein byreference. Further information on fatty amide carrier materials isdisclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No.4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat.No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S.Pat. No. 6,174,937, and British Patent GB 2 238 792, the disclosures ofeach of which are totally incorporated herein by reference.

Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO 96/14364, PCT Publication WO 97/33943, andPCT Publication WO 95/04760, the disclosures of each of which aretotally incorporated herein by reference.

Mixtures of fatty amide materials and isocyanate-derived materials canalso be employed as the ink carrier composition.

Additional suitable phase change ink carrier materials includeparaffins, microcrystalline waxes, polyethylene waxes, ester waxes,amide waxes, fatty acids, fatty alcohols, fatty amides and other waxymaterials, sulfonamide materials, resinous materials made from differentnatural sources (such as, for example, tall oil rosins and rosinesters), and many synthetic resins, oligomers, polymers and copolymers,such as ethylene/vinyl acetate copolymers, ethylene/acrylic acidcopolymers, ethylene/vinyl acetate/acrylic acid copolymers, copolymersof acrylic acid with polyamides, and the like, ionomers, and the like,as well as mixtures thereof. One or more of these materials can also beemployed in a mixture with a fatty amide material and/or anisocyanate-derived material.

In one specific embodiment, the phase change ink carrier comprises (a) apolyethylene wax, present in the ink in an amount in one embodiment ofat least about 25 percent by weight of the ink, in another embodiment ofat least about 30 percent by weight of the ink, and in yet anotherembodiment of at least about 37 percent by weight of the ink, and in oneembodiment of no more than about 60 percent by weight of the ink, inanother embodiment of no more than about 53 percent by weight of theink, and in yet another embodiment of no more than about 48 percent byweight of the ink, although the amount can be outside of these ranges;(b) a stearyl stearamide wax, present in the ink in an amount in oneembodiment of at least about 8 percent by weight of the ink, in anotherembodiment of at least about 10 percent by weight of the ink, and in yetanother embodiment of at least about 12 percent by weight of the ink,and in one embodiment of no more than about 32 percent by weight of theink, in another embodiment of no more than about 28 percent by weight ofthe ink, and in yet another embodiment of no more than about 25 percentby weight of the ink, although the amount can be outside of theseranges; (c) a dimer acid based tetra-amide that is the reaction productof dimer acid, ethylene diamine, and a long chain hydrocarbon havinggreater than thirty six carbon atoms and having a terminal carboxylicacid group, present in the ink in an amount in one embodiment of atleast about 10 percent by weight of the ink, in another embodiment of atleast about 13 percent by weight of the ink, and in yet anotherembodiment of at least about 16 percent by weight of the ink, and in oneembodiment of no more than about 32 percent by weight of the ink, inanother embodiment of no more than about 27 percent by weight of theink, and in yet another embodiment of no more than about 22 percent byweight of the ink, although the amount can be outside of these ranges;(d) a urethane resin derived from the reaction of two equivalents ofhydroabietyl alcohol and one equivalent of isophorone diisocyanate,present in the ink in an amount in one embodiment of at least about 6percent by weight of the ink, in another embodiment of at least about 8percent by weight of the ink, and in yet another embodiment of at leastabout 10 percent by weight of the ink, and in one embodiment of no morethan about 16 percent by weight of the ink, in another embodiment of nomore than about 14 percent by weight of the ink, and in yet anotherembodiment of no more than about 12 percent by weight of the ink,although the amount can be outside of these ranges; (e) a urethane resinthat is the adduct of three equivalents of stearyl isocyanate and aglycerol-based propoxylate alcohol, present in the ink in an amount inone embodiment of at least about 2 percent by weight of the ink, inanother embodiment of at least about 3 percent by weight of the ink, andin yet another embodiment of at least about 4.5 percent by weight of theink, and in one embodiment of no more than about 13 percent by weight ofthe ink, in another embodiment of no more than about 10 percent byweight of the ink, and in yet another embodiment of no more than about7.5 percent by weight of the ink, although the amount can be outside ofthese ranges; and (f) an antioxidant, present in the ink in an amount inone embodiment of at least about 0.01 percent by weight of the ink, inanother embodiment of at least about 0.05 percent by weight of the ink,and in yet another embodiment of at least about 0.1 percent by weight ofthe ink, and in one embodiment of no more than about 1 percent by weightof the ink, in another embodiment of no more than about 0.5 percent byweight of the ink, and in yet another embodiment of no more than about0.3 percent by weight of the ink, although the amount can be outside ofthese ranges.

The ink carrier is present in the phase change ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 50 percent byweight of the ink, and in yet another embodiment of at least about 90percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 98 percent by weight of the ink, and in yet anotherembodiment of no more than about 95 percent by weight of the ink,although the amount can be outside of these ranges.

The phase change inks contain a colorant compound comprising three ormore moieties of the formula

wherein (A) each R₁, independently of the others, is (i) an alkyl oralkylene group, (ii) an aryl or arylene group, (iii) an arylalkyl orarylalkylene group, (iv) an alkylaryl or alkylarylene group, (v) a silylor silylene group, or (vi) a siloxy group, (B) each R₂, independently ofthe others, is (i) an alkyl or alkylene group, (ii) an aryl or arylenegroup, (iii) an arylalkyl or arylalkylene group, (iv) an alkylaryl oralkylarylene group, (v) a silyl or silylene group, (vi) a siloxy group,or (vii) a group of the formula

wherein r and s are each, independently of the other, integersrepresenting a number of repeat —CH₂— groups, (C) each R₃, independentlyof the others, is (i) an alkyl group, (ii) an aryl group, (iii) anarylalkyl group, or (iv) an alkylaryl group, (D) each X, independentlyof the others, is (i) a direct bond, (ii) an oxygen atom, (iii) a sulfuratom, (iv) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and (E) each Z,independently of the others, is (i) a hydrogen atom, (ii) a halogenatom, (iii) a nitro group, (iv) an alkyl group, (v) an aryl group, (vi)an arylalkyl group, (vii) an alkylaryl group, (viii) a group of theformula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, a silyl group, or a siloxy group, (ix) a sulfonyl groupof the formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group,an aryl group, an arylalkyl group, an alkylaryl group, a silyl group, ora siloxy group, or (x) a phosphoryl group of the formula —PO₃R₉₀ whereinR₉₀ is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, a silyl group, or a siloxy group, saidmoieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer. This colorant is present in the ink in any desiredor effective amount to obtain the desired color or hue, in oneembodiment of at least about 0.1 percent by weight of the ink, inanother embodiment of at least about 0.5 percent by weight of the ink,in yet another embodiment of at least about 1 percent by weight of theink, in still another embodiment of at least about 2 percent by weightof the ink, and in another embodiment of at least about 3 percent byweight of the ink, and in one embodiment of no more than about 20percent by weight of the ink, in another embodiment of no more thanabout 13 percent by weight of the ink, and in yet another embodiment ofno more than about 6 percent by weight of the ink, although the amountcan be outside of these ranges. The colorant as disclosed herein caneither be the sole colorant in the ink or can be present in combinationwith other colorants, such as dyes, pigments, mixtures thereof, and thelike.

The inks can also optionally contain an antioxidant. The optionalantioxidants of the ink compositions protect the images from oxidationand also protect the ink components from oxidation during the heatingportion of the ink preparation process. Specific examples of suitableantioxidants include NAUGUARD® 524, NAUGUARD® 76, and NAUGUARD® 512(commercially available from Uniroyal Chemical Company, Oxford, Conn.),IRGANOX® 1010 (commercially available from Ciba Geigy), and the like.When present, the optional antioxidant is present in the ink in anydesired or effective amount, in one embodiment of at least about 0.01percent by weight of the ink, in another embodiment of at least about0.1 percent by weight of the ink, and in yet another embodiment of atleast about 1 percent by weight of the ink, and in one embodiment of nomore than about 20 percent by weight of the ink, in another embodimentof no more than about 5 percent by weight of the ink, and in yet anotherembodiment of no more than about 3 percent by weight of the ink,although the amount can be outside of these ranges.

The inks can also optionally contain a viscosity modifier. Examples ofsuitable viscosity modifiers include aliphatic ketones, such asstearone, and the like. When present, the optional viscosity modifier ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.1 percent by weight of the ink, in anotherembodiment of at least about 1 percent by weight of the ink, and in yetanother embodiment of at least about 10 percent by weight of the ink,and in one embodiment of no more than about 99 percent by weight of theink, in another embodiment of no more than about 30 percent by weight ofthe ink, and in yet another embodiment of no more than about 15 percentby weight of the ink, although the amount can be outside of theseranges.

Other optional additives to the inks include clarifiers, such as UNIONCAMP® X37-523-235 (commercially available from Union Camp), in an amountin one embodiment of at least about 0.01 percent by weight of the ink,in another embodiment of at least about 0.1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, tackifiers, such as FORAL® 85, a glycerol esterof hydrogenated abietic (rosin) acid (commercially available fromHercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin)acid (commercially available from Hercules), CELLOLYN® 21, ahydroabietic (rosin) alcohol ester of phthalic acid (commerciallyavailable from Hercules), ARAKAWA KE-311 and KE-100 Resins,triglycerides of hydrogenated abietic (rosin) acid (commerciallyavailable from Arakawa Chemical Industries, Ltd.), synthetic polyterpeneresins such as NEVTAC® 2300, NEVTAC® 100, and NEVTAC® 80 (commerciallyavailable from Neville Chemical Company), WINGTACK® 86, a modifiedsynthetic polyterpene resin (commercially available from Goodyear), andthe like, in an amount in one embodiment of at least about 0.1 percentby weight of the ink, in another embodiment of at least about 5 percentby weight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 98 percent by weight of the ink, in another embodiment of no morethan about 75 percent by weight of the ink, and in yet anotherembodiment of no more than about 50 percent by weight of the ink,although the amount can be outside of these range, adhesives, such asVERSAMID® 757, 759, or 744 (commercially available from Henkel), in anamount in one embodiment of at least about 0.1 percent by weight of theink, in another embodiment of at least about 1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, plasticizers, such as UNIPLEX® 250(commercially available from Uniplex), the phthalate ester plasticizerscommercially available from Monsanto under the trade name SANTICIZER®,such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate(SANTICIZER® 278), triphenyl phosphate (commercially available fromMonsanto), KP-140®, a tributoxyethyl phosphate (commercially availablefrom FMC Corporation), MORFLEX® 150, a dicyclohexyl phthalate(commercially available from Morflex Chemical Company Inc.), trioctyltrimellitate (commercially available from Eastman Kodak Co.), and thelike, in an amount in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 2percent by weight of the ink, and in one embodiment of no more thanabout 50 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 10 percent by weight of the ink,although the amount can be outside of these ranges, and the like.

The ink compositions in one embodiment have melting points of no lowerthan about 50° C., in another embodiment of no lower than about 70° C.,and in yet another embodiment of no lower than about 80° C., and havemelting points in one embodiment of no higher than about 160° C., inanother embodiment of no higher than about 140° C., and in yet anotherembodiment of no higher than about 100° C., although the melting pointcan be outside of these ranges.

The ink compositions generally have melt viscosities at the jettingtemperature (in one embodiment no lower than about 75° C., in anotherembodiment no lower than about 100° C., and in yet another embodiment nolower than about 120° C., and in one embodiment no higher than about180° C., and in another embodiment no higher than about 150° C.,although the jetting temperature can be outside of these ranges) in oneembodiment of no more than about 30 centipoise, in another embodiment ofno more than about 20 centipoise, and in yet another embodiment of nomore than about 15 centipoise, and in one embodiment of no less thanabout 2 centipoise, in another embodiment of no less than about 5centipoise, and in yet another embodiment of no less than about 7centipoise, although the melt viscosity can be outside of these ranges.

The ink compositions can be prepared by any desired or suitable method.For example, the ink ingredients can be mixed together, followed byheating, to a temperature in one embodiment of at least about 100° C.,and in one embodiment of no more than about 140° C., although thetemperature can be outside of these ranges, and stirring until ahomogeneous ink composition is obtained, followed by cooling the ink toambient temperature (typically from about 20 to about 25° C.). The inksare solid at ambient temperature. In a specific embodiment, during theformation process, the inks in their molten state are poured into moldsand then allowed to cool and solidify to form ink sticks.

The inks can be employed in apparatus for direct printing ink jetprocesses and in indirect (offset) printing ink jet applications.Another embodiment disclosed herein is directed to a process whichcomprises incorporating an ink as disclosed herein into an ink jetprinting apparatus, melting the ink, and causing droplets of the meltedink to be ejected in an imagewise pattern onto a recording substrate. Adirect printing process is also disclosed in, for example, U.S. Pat. No.5,195,430, the disclosure of which is totally incorporated herein byreference. Yet another embodiment disclosed herein is directed to aprocess which comprises incorporating an ink as disclosed herein into anink jet printing apparatus, melting the ink, causing droplets of themelted ink to be ejected in an imagewise pattern onto an intermediatetransfer member, and transferring the ink in the imagewise pattern fromthe intermediate transfer member to a final recording substrate. In aspecific embodiment, the intermediate transfer member is heated to atemperature above that of the final recording sheet and below that ofthe melted ink in the printing apparatus. An offset or indirect printingprocess is also disclosed in, for example, U.S. Pat. No. 5,389,958, thedisclosure of which is totally incorporated herein by reference. In onespecific embodiment, the printing apparatus employs a piezoelectricprinting process wherein droplets of the ink are caused to be ejected inimagewise pattern by oscillations of piezoelectric vibrating elements.Inks as disclosed herein can also be employed in other hot melt printingprocesses, such as hot melt acoustic ink jet printing, hot melt thermalink jet printing, hot melt continuous stream or deflection ink jetprinting, and the like. Phase change inks as disclosed herein can alsobe used in printing processes other than hot melt ink jet printingprocesses.

Any suitable substrate or recording sheet can be employed, includingplain papers such as XEROX® 4024 papers, XEROX® Image Series papers,Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coatedpapers such as Sharp Company silica coated paper, JuJo paper, HAMMERMILLLASERPRINT® paper, and the like, transparency materials, fabrics,textile products, plastics, polymeric films, inorganic substrates suchas metals and wood, and the like.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and the claims are not limited to thematerials, conditions, or process parameters set forth in theseembodiments. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I Part A: Dipentaerythritol Hexaanthranilate Synthesis

Into a 1 liter round bottom flask equipped with mechanical stirrer,dropping funnel, and thermometer, was charged dipentaerythritol (76.2grams, 0.03 mol; obtained from Sigma-Aldrich, Milwaukee, Wis.), isatoicanhydride (342 grams, 2.1 mol; obtained from Sigma-Aldrich),1,4-diazabicyclo(2.2.2)octane (DABCO) (33 grams, 0.3 mol; obtained fromSigma-Aldrich), and dimethylformamide (500 milliliters). The mixture wasstirred and heated to 120° C. for a period of about 16 hours. Themixture was then cooled to room temperature and methanol (2 liters) wasadded. Deionized water (100 milliliters) was subsequently added, causingthe solution to turn cloudy. This solution was stirred for four hoursand then filtered, washed with 5×200 milliliters of methanol, and ovendried at 60° C. to yield 135 grams of a beige solid.

Part B: Dodecyl Pyridone Synthesis

Into a 2 liter Erlenmeyer flask equipped with magnetic stirring wascharged dodecylamine (185.0 grams, 1.0 mol; obtained from Sigma-Aldrich)followed with ethyl cyanoacetate (ECA, 135.5 grams, 1.20 mol; obtainedfrom Sigma-Aldrich). The mixture was then heated to 140° C. and stirredat this temperature for 1 hour, during which time the ethanol by-productwas allowed to distill away. Thereafter, to the hot reaction mixturestirring at 140° C. internal temperature was sequentially addeddimethylformamide (DMF; 250 milliliters), ethyl acetoacetate (EAA; 266.0grams, 2.0 mol; obtained from Sigma-Aldrich), and piperazine (PIP; 129.0grams, 1.5 mol; obtained from Sigma-Aldrich). The mixture was thenheated to 110° C. for 4 hours. The mixture was then allowed to cool toroom temperature and was poured slowly into a mixture of deionized water(1,500 milliliters), methanol (3,500 milliliters), and concentratednitric acid (270.0 grams, 3.0 mol). A white precipitate formedimmediately and was allowed to stir at room temperature for 3 hours, andthen was filtered and washed with a 70:30 (v/v) mixture ofmethanol/deionized water (500 milliliters). The precipitate was thenoven dried at 60° C. to give 270.5 grams of an off white solid at 85percent yield.

Part C: Dye Coupling

Into a 500 milliliter round bottom flask equipped with mechanicalstirrer, dropping funnel, and thermometer was charged under agitationthe hexaanthranilate prepared in Part A above (14.5 grams, 0.015 mol),followed with a prepared solution containing 150 milliliters of glacialacetic acid, 50 milliliters of deionized water, and 10 milliliters ofconcentrated sulfuric acid. The resulting dark, slightly cloudy solutionwas chilled to an internal temperature of 5° C. Nitrosylsulfuric acid(NSA, commercial solution containing 40 percent by weight NSA insulfuric acid, obtained from Sigma-Aldrich Co., Milwaukee, Wis., 29.2grams, 0.092 mol) was charged into the dropping funnel and then drippedslowly into the solution at a rate whereby the internal temperature wasmaintained between 0° C. and 10° C. After 15 minutes, the NSA additionwas completed and the mixture was stirred for an additional 15 minuteswhile being cooled at 0° C. An aqueous urea solution (20 milliliters/2Molar, 0.04 mol) was then added to the mixture to quench any residualNSA reagent and the mixture was stirred for 15 more minutes.

A coupling solution of the dodecyl pyridone prepared in Part B above wasprepared in a 2 liter kettle equipped with mechanical stirrer. Into thisvessel was charged dodecyl pyridone (31.8 grams, 0.1 mol) prepared asdescribed in Part B above, followed with a solution containing 500milliliters of isopropanol and 500 milliliters of deionized water.Diethylaminoethanol (39.0 grams, 0.33 mol; obtained from Sigma-Aldrich)was then added, and the solution cleared, leaving a slightly cloudybeige solution.

The cold diazonium salt solution was then slowly poured into thevigorously stirred dodecyl pyridone coupling solution. A bright yellowprecipitate formed immediately, and after complete addition of thediazonium salt solution the yellow slurry was stirred for an additional1 hour.

The yellow slurry thus formed was vacuum filtered and the yellow dyecake was then washed in the funnel with a 50:50 mixture of isopropanoland deionized water (3×250 milliliters) and then water (250milliliters). The filter cake was then redispersed multiple times indeionized water (250 milliliters), stirred for 30 minutes, andrefiltered until the pH of the resulting filtrate was greater than 5.0and the conductivity of the filtrate was low. The filter cake was giventwo final rinses with methanol (250 milliliters). The cake was thendried in a vacuum-oven at 40° C. for 36 hours, affording 39.8 grams ofthe crude product as a bright yellow powder. If desired, this materialcan be further purified by recrystallization or reprecipitation. Theproduct thus obtained was believed to be of the formula

EXAMPLE II Part A: Pentaerythritol Tetraanthranilate Synthesis

Into a 1 liter round bottom flask equipped with mechanical stirrer,dropping funnel, and thermometer was charged pentaerythritol (68.5grams, 0.5 mol; obtained from Sigma-Aldrich), isatoic anhydride (407.0grams, 2.5 mol), 1,4-diazabicyclo(2.2.2)octane (DABCO) (33 grams, 0.3mol), and dimethylformamide (400 milliliters). The mixture was stirredand heated to 120° C. for a period of about 2 hours. The mixture wasthen cooled to room temperature and methanol (2 liters) added. Deionizedwater (300 milliliters) was subsequently added, causing the solution toform a thick suspension. Methanol (700 milliliters) was added to enablestirring of the thick slurry. The solution was stirred for 3 hours andthen filtered, washed with 5×200 milliliters of methanol, and oven driedat 60° C. to yield 239 grams of a beige solid at 78 percent yield.

Part B: Stearyl Pyridone Synthesis

Into a 2 liter Erlenmeyer flask equipped with magnetic stirring wascharged stearylamine (118 g, 0.44 mol; obtained from Sigma-Aldrich) andethyl cyanoacetate (ECA, 45.2 grams, 0.4 mol). The mixture was heated to120° C. for 90 minutes, after which ethyl acetoacetate (EAA, 114 grams,0.88 mol), piperidine (PIP; 70 grams, 0.82 mol), and dimethylformamide(DMF; 140 milliliters) were added. The mixture was heated to 120° C. for4 hours. The mixture was then allowed to cool to room temperature andwas poured slowly into well stirred methanol (1,200 milliliters), whichcontained concentrated hydrochloric acid (100 milliliters). Theresulting suspension was allowed to stir for 10 minutes, and was thenfiltered and washed with 3×200 milliliter portions of methanol. Theresulting solid was oven dried at 60° C. to give 91.3 grams of a beigepowder at 57 percent yield.

Part C: Dye Coupling

Into a 500 milliliter round bottom flask equipped with mechanicalstirrer, dropping funnel, and thermometer was charged under agitationtetrakisanthranilate (12.2 grams, 0.02 mol), prepared as described inPart A above, followed with a prepared solution containing 150milliliters of glacial acetic acid, 50 milliliters of deionized water,and 12 milliliters of concentrated sulfuric acid. The resulting dark,slightly cloudy solution was chilled to an internal temperature of 5° C.Nitrosylsulfuric acid (NSA, commercial solution containing 40 percent byweight NSA in sulfuric acid, obtained from Sigma-Aldrich Co., Milwaukee,Wis., 26.0 grams, 0.082 mol) was charged into the dropping funnel andthen dripped slowly into the solution at a rate whereby the internaltemperature was maintained between 0° C. and 10° C. After 15 minutes,the NSA addition was completed and the mixture was stirred for anadditional-15 minutes while being cooled at 0° C. An aqueous ureasolution (20 milliliters/2 Molar, 0.04 mol) was then added to themixture to quench any residual NSA reagent and the mixture was stirredfor 15 more minutes.

A coupling solution of stearyl pyridone was prepared in a 2 liter kettleequipped with mechanical stirrer. Into this vessel was charged stearylpyridone (30.3 grams, 0.075 mol) prepared as described in Part B above,followed with a solution containing 500 milliliters of isopropanol and500 milliliters of deionized water. Diethylaminoethanol (39.0 grams,0.33 mol) was then added, and the solution cleared, leaving a slightlycloudy beige solution.

The cold diazonium salt solution was then slowly poured into thevigorously stirred stearyl pyridone coupling solution. A bright yellowprecipitate was formed immediately, and after complete addition of thediazonium salt solution, the yellow slurry was stirred for an additional1 hour.

The yellow slurry was vacuum filtered, and the yellow dye cake was thenwashed in the funnel with a 50:50 mixture of isopropanol and deionizedwater (3×250 milliliters) and then water (250 milliliters). The filtercake was then redispersed multiple times in deionized water (250milliliters), stirred for 30 minutes, and filtered until the pH of theresulting filtrate was greater than 5.0 and the conductivity of thefiltrate was low. The filter cake was given two final rinses withmethanol (250 milliliters). The cake was then dried in a vacuum-oven at40° C. for 36 hours, affording, 39.5 grams of the crude product as adull yellow powder. If desired, this material can be further purified byrecrystallization or reprecipitation. The product thus obtained wasbelieved to be of the formula

EXAMPLE III Part A: Dipentaerythritol Hexaanthranilate Synthesis

The anthranilate was prepared as described in Part A of Example I.

Part B: Stearyl Pyridone Synthesis

The pyridone was prepared as described in Part B of Example II.

Part C: Dye Coupling

Into a 500 milliliter round bottom flask equipped with mechanicalstirrer, dropping funnel, and thermometer was charged under agitationthe hexaanthranilate (14.5 grams, 0.015 mol), prepared as described inPart A of Example I, followed with a prepared solution containing 150milliliters of glacial acetic acid, 50 milliliters of deionized water,and 15 milliliters of concentrated sulfuric acid. The resulting dark,slightly cloudy solution was chilled to an internal temperature of 5° C.Nitrosylsulfuric acid (NSA, commercial solution containing 40 percent byweight NSA in sulfuric acid, obtained from Sigma-Aldrich Co., Milwaukee,Wis., 29.2 grams, 0.092 mol) was charged into the dropping funnel andthen dripped slowly into the solution at a rate whereby the internaltemperature was maintained between 0° C. and 10° C. After 15 minutes,the NSA addition was completed and the mixture was stirred for anadditional 15 minutes while being cooled at 0° C. An aqueous ureasolution (20 milliliters/2 Molar, 0.04 mol) was then added to themixture to quench any residual NSA reagent and the mixture was stirredfor 15 more minutes.

A coupling solution of stearyl pyridone was prepared in a 2 liter kettleequipped with mechanical stirrer. Into this vessel was charged stearylpyridone (42.6 grams, 0.079 mol) prepared as described in Part B ofExample II, followed with a solution consisting of 500 milliliters ofisopropanol and 500 milliliters of deionized water. Diethylaminoethanol(39.0 grams, 0.33 mol) was then added and the solution cleared, leavinga slightly cloudy brown solution.

The cold diazonium salt solution was then slowly poured into thevigorously stirred stearyl pyridone coupling solution. A bright yellowprecipitate formed immediately, and after complete addition of thediazonium salt solution the yellow slurry was stirred an additional 1hour.

The yellow slurry was vacuum filtered, and the yellow dye cake was thenwashed in the funnel with a 50:50 mixture of isopropanol and deionizedwater (3×250 milliliters) and then water (250 milliliters). The filtercake was then redispersed multiple times in deionized water (250milliliters), stirring for 30 minutes, and filtered until the pH of theresulting filtrate was greater than 5.0 and the conductivity of thefiltrate was low. The filter cake was given two final rinses withmethanol (250 milliliters). The cake was then dried in a vacuum-oven at40° C. for 36 hours, affording 44.1 grams of the crude product as abright yellow powder. If desired, this material can be further purifiedby recrystallization or reprecipitation. The product thus obtained wasbelieved to be of the formula

EXAMPLE IV Part A: Stearyl Anthranilate Synthesis

Into a 4 liter beaker equipped with magnetic stirrer, dropping funnel,and thermometer, was charged stearyl alcohol (270.0 grams, 1.0 mol;obtained from Sigma-Aldrich), isatoic anhydride (244.0 grams, 1.5 mol),1,4-diazabicyclo(2.2.2)octane (DABCO) (56 grams, 0.5 mol), anddimethylformamide (750 milliliters). The mixture was stirred and heatedto 120° C. for a period of about 2 hours. The mixture was then cooled to50° C., and methanol (3 liters) was added. A thick white precipitateformed, which was filtered and then washed with 3×1 liter portions ofmethanol and oven dried at 60° C. to yield 295.8 grams of a beige solidat 76 percent yield.

Part B: Tripyridone Synthesis

Into a 125 milliliter Erlenmeyer flask equipped with magnetic stirringwas charged tris(2-aminoethyl)amine (48.0 g, 0.33 mol; obtained fromSigma-Aldrich) and ethyl cyanoacetate (ECA, 135.0 grams, 1.20 mol). Themixture was then heated to 150° C. and stirred at this temperature for 1hour, during which time the ethanol by-product was allowed to distillaway (˜15 milliliters). To the hot reaction mixture was sequentiallyadded ethyl acetoacetate (EAA, 390.0 grams, 3.0 mol), piperazine (PIP;172.0 grams, 2.0 mol) and dimethylformamide (300 milliliters). Themixture was then heated to 120° C. for 5 hours, cooled, and then pouredslowly into a mixture of deionized water (700 milliliters), methanol(2,100 milliliters), and concentrated nitric acid (258 grams, 4.0 mol).A white precipitate formed immediately, and the precipitate was allowedto stir at room temperature for 3 hours, and then was filtered andwashed with a 50:50 (v/v) mixture of methanol/deionized water (5×500milliliters). The precipitate was then oven dried at 60° C. to give 130grams of an off white solid at 72 percent yield.

Part C: Dye Coupling

Into a 500 milliliter round bottom flask equipped with mechanicalstirrer, dropping funnel, and thermometer was charged under agitationthe stearyl anthranilate (35.8 grams, 0.092 mol) prepared as describedin Part A above, followed with a prepared solution containing 100milliliters of glacial acetic acid, 100 milliliters ofdodecylbenzenesulfonic acid, and 50 milliliters of propionic acid(obtained from Sigma-Aldrich). The resulting dark, slightly cloudysolution was chilled to an internal temperature of 5° C.Nitrosylsulfuric acid (NSA, commercial solution containing 40 percent byweight NSA in sulfuric acid, obtained from Sigma-Aldrich Co., Milwaukee,Wis., 28.3 grams, 0.089 mol) was charged into the dropping funnel andthen dripped slowly into the solution at a rate whereby the internaltemperature was maintained between 0° C. and 10° C. After 15 minutes,the NSA addition was completed and the mixture was stirred for anadditional 15 minutes while being cooled at 0° C. An aqueous ureasolution (20 milliliters/2 Molar, 0.04 mol) was then added to themixture to quench any residual NSA reagent and the mixture was stirredfor 15 more minutes.

A coupling solution of tripyridone was prepared in a 2 liter kettleequipped with mechanical stirrer. Into this vessel was chargedtripyridone (16.35 grams, 0.03 mol) prepared as described in Part Babove, followed with a solution consisting of 650 milliliters ofisopropanol and 250 milliliters of deionized water. Diethylaminoethanol(23.1 grams, 0.2 mol) was then added, and the solution cleared, leavinga slightly cloudy brown solution.

The cold diazonium salt solution was then slowly poured into thevigorously stirred tripyridone coupling solution. A bright yellowprecipitate was formed immediately, and after complete addition of thediazonium salt solution, the yellow slurry was stirred for an additional1 hour.

The resulting yellow slurry was vacuum filtered and the yellow dye cakewas then washed in the funnel with a 50:50 mixture of isopropanol anddeionized water (3×250 milliliters) and then water (250 milliliters).The filter cake was then redispersed multiple times in deionized water(250 milliliters), stirred for 30 minutes, and filtered until the pH ofthe resulting filtrate was greater than 5.0 and the conductivity of thefiltrate was low. The filter cake was given two final rinses withmethanol (250 milliliters). The cake was then dried in a vacuum-oven at40° C. for 36 hours, affording 52.8 grams of the crude product as abright yellow powder. If desired, this material can be further purifiedby recrystallization or reprecipitation. The product thus obtained wasbelieved to be of the formula

EXAMPLE V Part A: Triethanolamine Trianthranilate Synthesis

Into a 1 liter round bottom flask-equipped with mechanical stirrer,dropping funnel, and thermometer was charged triethanolamine (149.2grams, 1.0 mol; obtained from Sigma-Aldrich), isatoic anhydride (520.0grams, 3.5 mol), 1,4-diazabicyclo(2.2.2)octane (DABCO) (45.0 grams, 0.4mol), and dimethylformamide (1,500 milliliters). The mixture was stirredand heated to 120° C. for a period of about 2 hours. The mixture wasthen cooled to room temperature, and methanol (2 liters) was added.Deionized water (1 liter) was added, causing the solution to turncloudy. This solution was stirred for 2 hours, and then filtered, washedwith 5×250 milliliters of methanol, and oven dried at 60° C. to yield506 grams of a beige solid.

Part B: Stearyl Pyridone Synthesis

The pyridone was prepared as described in Part B of Example II.

Part C: Dye Coupling

Into a 500 milliliter round bottom flask equipped with mechanicalstirrer, dropping funnel, and thermometer was charged under agitationthe trianthranilate (15.2 grams, 0.03 mol) prepared as described in PartA, followed with a prepared solution containing 96 milliliters ofglacial acetic acid, 40 milliliters of deionized water, and 25milliliters of concentrated sulfuric acid. The resulting dark, slightlycloudy solution was chilled to an internal temperature of 5° C.Nitrosylsulfuric acid (NSA, commercial solution containing 40 percent byweight NSA in sulfuric acid, obtained from Sigma-Aldrich Co., Milwaukee,Wis., 28.3 grams, 0.089 mol) was charged into the dropping funnel andthen dripped slowly into the solution at a rate whereby the internaltemperature was maintained between 0° C. and 10° C. After 15 minutes,the NSA addition was completed and the mixture was stirred for anadditional 15 minutes while being cooled at 0° C. An aqueous ureasolution (20 milliliters/2 Molar, 0.04 mol) was then added to themixture to quench any residual NSA reagent and the mixture was stirredfor 15 more minutes.

A coupling solution of stearyl pyridone was prepared in a 2 liter kettleequipped with mechanical stirrer. Into this vessel was charged stearylpyridone (37.4 grams, 0.092 mol) prepared as described in Part B ofExample II, followed with a solution containing 250 milliliters ofisopropanol and 250 milliliters of deionized water. Diethylaminoethanol(26.0 grams, 0.22 mol) was then added, and the solution cleared, leavinga slightly cloudy brown solution.

The cold diazonium salt solution was then slowly poured into thevigorously stirred stearyl pyridone coupling solution. A bright yellowprecipitate formed immediately, and after complete addition of thediazonium salt solution, the yellow slurry was stirred an additional 1hour.

The yellow slurry was vacuum filtered, and the yellow dye cake was thenwashed in the funnel with a 50:50 mixture of isopropanol and deionizedwater (3×250 milliliters) and then water (250 milliliters). The filtercake was then redispersed multiple times in deionized water (250milliliters), stirred for 30 minutes, and filtered until the pH of theresulting filtrate was greater than 5.0 and the conductivity of thefiltrate was low. The filter cake was given two final rinses withmethanol (250 milliliters). The cake was then dried in a vacuum-oven at40° C. for 36 hours, affording 55.1 grams of the crude product as abright yellow powder. If desired, this material can be further purifiedby recrystallization or reprecipitation. The product thus obtained wasbelieved to be of the formula

EXAMPLE VI Part A: Polyanthranilate Synthesis

A polyanthranilate is prepared as described in Part A of Example Iexcept that poly(vinyl alcohol) is used instead of dipentaerythritol,said poly(vinyl alcohol) having from about 6 to about 30 pendanthydroxyl groups. Stoichiometry of the additional reagents is modifiedaccordingly. The resulting product has from about 6 to about 30 pendantanthranilate groups.

Part B: Dodecyl Pyridone Synthesis

The pyridone is prepared as described in Part B of Example I.

Part C: Dye Coupling

Diazo coupling is effected by the procedure described in Example I,using approximately stoichiometrically equivalent amounts ofanthranilate and pyridone moieties, to form a polymeric compound havingpendant therefrom from about 6 to about 30 groups of the formula

EXAMPLE VII Part A: Stearyl Anthranilate Synthesis

The pyridone is prepared as described in Part A of Example IV.

Part B: Polypyridone Synthesis

A polypyridone is prepared as in Part A of Example IV except thatpoly(vinylamine) is used instead of dodecyl aniline, saidpoly(vinylamine) having from about 6 to about 30 pendant —NH₂ groups.Stoichiometry of the additional reagents is modified accordingly. Theresulting product has from about 6 to about 30 pendant pyridone groups.

Part C: Dye Coupling

Diazo coupling is effected by the procedure described in Example IV,using approximately stoichiometrically equivalent amounts ofanthranilate and pyridone moieties, to form a polymeric compound havingpendant therefrom from about 6 to about 30 groups of the formula

INK EXAMPLE 1

A phase change ink is prepared as follows. In a stainless steel beakerare combined 430 grams of polyethylene wax (PE 655, available from BakerPetrolite, Tulsa, Okla., of the formula CH₃(CH₂)₅₀CH₃), 194 grams ofstearyl stearomide wax (KEMAMIDE® S-180, available from CromptonCorporation, Greenwich, Conn.), 219 grams of a tetra-amide resinobtained from the reaction of one equivalent of a C-36 dimer acidavailable from Uniqema, New Castle, Del. with two equivalents ofethylene diamine and UNICID® 700 (available from Baker Petrolite, Tulsa,Okla., a long chain hydrocarbon having a terminal carboxylic acidgroup), prepared as described in Example 1 of U.S. Pat. No. 6,174,937,the disclosure of which is totally incorporated herein by reference, 77grams of a urethane resin obtained from the reaction of two equivalentsof ABITOL® E hydroabietyl alcohol (available from Hercules Inc.,Wilmington, Del.) and one equivalent of isophorone diisocyanate,prepared as described in Example 1 of U.S. Pat. No. 5,782,966, thedisclosure of which is totally incorporated herein by reference, 46grams of a urethane resin that is the adduct of three equivalents ofstearyl isocyanate and a glycerol-based alcohol, prepared as describedin Example 4 of U.S. Pat. No. 6,309,453, the disclosure of which istotally incorporated herein by reference, and 2.0 gram of NAUGUARD® 445antioxidant (available from Uniroyal Chemical Co., Middlebury, Conn.).The materials are melted together at a temperature of about 140° C. inan oven, then blended by stirring in a temperature controlled mantle atabout 135° C. for about 0.5 hour. To this mixture is then added about 20grams of the colorant prepared as described in Example I. After stirringfor about 3 additional hours, the yellow ink thus formed is filteredthrough a heated MOTTO apparatus (obtained from Mott Metallurgical)using #3 Whatman filter paper and a pressure of about 15 pounds persquare inch. The filtered phase change ink is poured into molds andallowed to solidify to form ink sticks.

INK EXAMPLES 2 TO 7

The process of Ink Example 1 is repeated except that the colorants ofExamples II through VII are substituted for the colorant of Example I.

Other embodiments and modifications of the present invention may occurto those of ordinary skill in the art subsequent to a review of theinformation presented herein; these embodiments and modifications, aswell as equivalents thereof, are also included within the scope of thisinvention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A compound comprising three or more moieties of the formula

wherein (A) each R₁, independently of the others, is (i) an alkyl oralkylene group, (ii) an aryl or arylene group, (iii) an arylalkyl orarylalkylene group, (iv) an alkylaryl or alkylarylene group, (v) a silylor silylene group, or (vi) a siloxy group, (B) each R₂, independently ofthe others, is (i) an alkyl or alkylene group, (ii) an aryl or arylenegroup, (iii) an arylalkyl or arylalkylene group, (iv) an alkylaryl oralkylarylene group, (v) a silyl or silylene group, (vi) a siloxy group,or (vii) a group of the formula

wherein r and s are each, independently of the other, integersrepresenting a number of repeat —CH₂— groups, (C) each R₃, independentlyof the others, is (i) an alkyl group, (ii) an aryl group, (iii) anarylalkyl group, or (iv) an alkylaryl group, (D) each X, independentlyof the others, is (i) a direct bond, (ii) an oxygen atom, (iii) a sulfuratom, (iv) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and (E) each Z,independently of the others, is (i) a hydrogen atom, (ii) a halogenatom, (iii) a nitro group, (iv) an alkyl group, (v) an aryl group, (vi)an arylalkyl group, (vii) an alkylaryl group, (viii) a group of theformula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, a silyl group, or a siloxy group, (ix) a sulfonyl groupof the formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group,an aryl group, an arylalkyl group, an alkylaryl group, a silyl group, ora siloxy group, or (x) a phosphoryl group of the formula —PO₃R₉₀ whereinR₉₀ is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, a silyl group, or a siloxy group; saidmoieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer.
 2. A compound according to claim 1 wherein thecompound contains four or more moieties of the formula


3. A compound according to claim 1 wherein the moieties are linked tothe central atom or group of atoms or bonded to the polymer through theR₁ group and wherein the moieties are of the formula


4. A compound according to claim 1 wherein the moieties are linked tothe central atom or group of atoms or bonded to the polymer through theR₂ group and wherein the moieties are of the formula


5. A compound according to claim 1 wherein the moieties are bonded to asingle central atom.
 6. A compound according to claim 5 of the formula


7. A compound according to claim 1 wherein the moieties are bonded to amonomeric group of atoms.
 8. A compound according to claim 1 wherein themoieties are bonded to an oligomer or polymer.
 9. A compound accordingto claim 8 wherein the oligomer or polymer has no more than about 20repeat monomer units.
 10. A compound according to claim 8 wherein theoligomer or polymer has at least about 10 repeat monomer units.
 11. Acompound according to claim 8 wherein the oligomer or polymer has atleast about 6 of the moieties pendant therefrom and wherein the oligomeror polymer has no more than about 30 of the moieties pendant therefrom.12. A compound according to claim 8 wherein the oligomer or polymer hasat least about 10 of the moieties pendant therefrom and wherein theoligomer or polymer has no more than about 20 of the moieties pendanttherefrom.
 13. A compound according to claim 1 wherein R₃ is methyl. 14.A compound according to claim 1 wherein the colorant is


15. A compound according to claim 1 wherein R₁ is an alkyl or alkylenegroup and R₂ is an alkyl or alkylene group.
 16. A compound according toclaim 15 wherein at least one of R₁ and R₂ is a linear alkyl or alkylenegroup.
 17. A compound according to claim 15 wherein at least one of R₁and R₂ is a branched alkyl or alkylene group.
 18. A compound accordingto claim 15 wherein at least one of R₁ and R₂ is a saturated alkyl oralkylene group.
 19. A compound according to claim 15 wherein at leastone of R₁ and R₂ is an unsaturated alkyl or alkylene group.
 20. Acompound according to claim 15 wherein at least one of R₁ and R₂ is anunsubstituted alkyl or alkylene group.
 21. A compound according to claim15 wherein at least one of R₁ and R₂ is a substituted alkyl or alkylenegroup.
 22. A compound according to claim 15 wherein at least one of R₁and R₂ is an alkyl or alkylene group wherein hetero atoms selected fromoxygen, nitrogen, sulfur, silicon, or phosphorus are present in thealkyl or alkylene group.
 23. A compound according to claim 15 wherein atleast one of R₁ and R₂ is an alkyl or alkylene group wherein no heteroatoms are present in the alkyl or alkylene group.
 24. A compoundaccording to claim 15 wherein at least one of R₁ and R₂ is an alkyl oralkylene group having at least 8 carbon atoms.
 25. A phase change inkcomposition comprising a phase change ink carrier and a colorantcompound comprising three or more moieties of the formula

wherein (A) each R₁, independently of the others, is (i) an alkyl oralkylene group, (ii) an aryl or arylene group, (iii) an arylalkyl orarylalkylene group, (iv) an alkylaryl or alkylarylene group, (v) a silylor silylene group, or (vi) a siloxy group, (B) each R₂, independently ofthe others, is (i) an alkyl or alkylene group, (ii) an aryl or arylenegroup, (iii) an arylalkyl or arylalkylene group, (iv) an alkylaryl oralkylarylene group, (v) a silyl or silylene group, (vi) a siloxy group,or (vii) a group of the formula

wherein r and s are each, independently of the other, integersrepresenting a number of repeat —CH₂— groups, (C) each R₃, independentlyof the others, is (i) an alkyl group, (ii) an aryl group, (iii) anarylalkyl group, or (iv) an alkylaryl group, (D) each X, independentlyof the others, is (i) a direct bond, (ii) an oxygen atom, (iii) a sulfuratom, (iv) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and (E) each Z,independently of the others, is (i) a hydrogen atom, (ii) a halogenatom, (iii) a nitro group, (iv) an alkyl group, (v) an aryl group, (vi)an arylalkyl group, (vii) an alkylaryl group, (viii) a group of theformula—

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, a silyl group, or a siloxy group, (ix) a sulfonyl groupof the formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group,an aryl group, an arylalkyl group, an alkylaryl group, a silyl group, ora siloxy group, or (x) a phosphoryl group of the formula —PO₃R₉₀ whereinR₉₀ is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, a silyl group, or a siloxy group; saidmoieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer.
 26. A phase change ink according to claim 25wherein the colorant compound contains four or more moieties of theformula


27. A phase change ink according to claim 25 wherein the moieties arelinked to the central atom or group of atoms or bonded to the polymerthrough the R₁ group and wherein the moieties are of the formula


28. A phase change ink according to claim 25 wherein the moieties arelinked to the central atom or group of atoms or bonded to the polymerthrough the R₂ group and wherein the moieties are of the formula


29. A phase change ink according to claim 25 wherein the moieties arebonded to a single central atom.
 30. A phase change ink according toclaim 29 of the formula


31. A phase change ink according to claim 25 wherein the moieties arebonded to a monomeric group of atoms.
 32. A phase change ink accordingto claim 25 wherein the moieties are bonded to an oligomer or polymer.33. A phase change ink according to claim 32 wherein the oligomer orpolymer has no more than about 20 repeat monomer units.
 34. A phasechange ink according to claim 32 wherein the oligomer or polymer has atleast about 10 repeat monomer units.
 35. A phase change ink according toclaim 32 wherein the oligomer or polymer has at least about 6 of themoieties pendant therefrom and wherein the oligomer or polymer has nomore than about 30 of the moieties pendant therefrom.
 36. A phase changeink according to claim 32 wherein the oligomer or polymer has at leastabout 10 of the moieties pendant therefrom and wherein the oligomer orpolymer has no more than about 20 of the moieties pendant therefrom. 37.A phase change ink according to claim 25 wherein R₃ is methyl.
 38. Aphase change ink according to claim 25 wherein the colorant is


39. A phase change ink according to claim 25 wherein R₁ is an alkyl oralkylene group and R₂ is an alkyl or alkylene group.
 40. A phase changeink according to claim 39 wherein at least one of R₁ and R₂ is a linearalkyl or alkylene group.
 41. A phase change ink according to claim 39wherein at least one of R₁ and R₂ is a branched alkyl or alkylene group.42. A phase change ink according to claim 39 wherein at least one of R₁and R₂ is a saturated alkyl or alkylene group.
 43. A phase change inkaccording to claim 39 wherein at least one of R₁ and R₂ is anunsaturated alkyl or alkylene group.
 44. A phase change ink according toclaim 39 wherein at least one of R₁ and R₂ is an unsubstituted alkyl oralkylene group.
 45. A phase change ink according to claim 39 wherein atleast one of R₁ and R₂ is a substituted alkyl or alkylene group.
 46. Aphase change ink according to claim 39 wherein at least one of R₁ and R₂is an alkyl or alkylene group wherein hetero atoms selected from oxygen,nitrogen, sulfur, silicon, or phosphorus are present in the alkyl oralkylene group.
 47. A phase change ink according to claim 39 wherein atleast one of R₁ and R₂ is an alkyl or alkylene group wherein no heteroatoms are present in the alkyl or alkylene group.
 48. A phase change inkaccording to claim 39 wherein at least one of R₁ and R₂ is an alkyl oralkylene group having at least 8 carbon atoms.
 49. A phase change inkaccording to claim 25 wherein the phase change ink carrier comprises amonoamide, a tetra-amide, or a mixture thereof.
 50. A phase change inkaccording to claim 25 wherein the phase change ink carrier comprises (a)stearyl stearamide, (b) a dimer acid based tetra-amide that is thereaction product of dimer acid, ethylene diamine, and stearic acid, or(c) mixtures thereof.
 51. A phase change ink according to claim 25wherein the phase change ink carrier comprises (a) stearyl stearamide,(b) a dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and a carboxylic acid having at least about 36carbon atoms, or (c) mixtures thereof.
 52. A phase change ink accordingto claim 25 wherein the phase change ink carrier comprises anisocyanate-derived material.
 53. A phase change ink according to claim25 wherein the phase change ink carrier comprises a mixture of one ormore amides and one or more isocyanate-derived materials.
 54. A phasechange ink according to claim 25 wherein the phase change ink carriercomprises one or more materials selected from paraffins,microcrystalline waxes, polyethylene waxes, ester waxes, amide waxes,fatty acids, fatty alcohols, fatty amides, sulfonamide materials, talloil rosins, rosin esters, ethylene/vinyl acetate copolymers,ethylene/acrylic acid copolymers, ethylene/vinyl acetate/acrylic acidcopolymers, copolymers of acrylic acid with polyamides, ionomers, andmixtures thereof.
 55. A phase change ink according to claim 25 whereinthe ink carrier comprises (a) a polyethylene wax, (b) a stearylstearamide wax, (c) a dimer acid based tetra-amide that is the reactionproduct of dimer acid, ethylene diamine, and a carboxylic acid having atleast about 36 carbon atoms, (d) a urethane resin derived from thereaction of two equivalents of hydroabietyl alcohol and one equivalentof isophorone diisocyanate, (e) a urethane resin that is the adduct ofthree equivalents of stearyl isocyanate and a glycerol-based alcohol,and (f) an antioxidant.
 56. A phase change ink according to claim 25wherein the colorant is present in the ink in an amount of at leastabout 0.1 percent by weight of the ink.
 57. A phase change ink accordingto claim 25 wherein the colorant is present in the ink in an amount ofno more than about 20 percent by weight of the ink.
 58. A phase changeink according to claim 25 wherein the ink has a melting point of nolower than about 70° C. and wherein the ink has a melting point of nohigher than about 140° C.
 59. A process which comprises (1)incorporating into an ink jet printing apparatus a phase change inkcomposition comprising a phase change ink carrier and a colorantcompound comprising three or more moieties of the formula

wherein (A) each R₁, independently of the others, is (i) an alkyl oralkylene group, (ii) an aryl or arylene group, (iii) an arylalkyl orarylalkylene group, (iv) an alkylaryl or alkylarylene group, (v) a silylor silylene group, or (vi) a siloxy group, (B) each R₂, independently ofthe others, is (i) an alkyl or alkylene group, (ii) an aryl or arylenegroup, (iii) an arylalkyl or arylalkylene group, (iv) an alkylaryl oralkylarylene group, (v) a silyl or silylene group, (vi) a siloxy group,or (vii) a group of the formula

wherein r and s are each, independently of the other, integersrepresenting a number of repeat —CH₂— groups, (C) each R₃, independentlyof the others, is (i) an alkyl group, (ii) an aryl group, (iii) anarylalkyl group, or (iv) an alkylaryl group, (D) each X, independentlyof the others, is (i) a direct bond, (ii) an oxygen atom, (iii) a sulfuratom, (iv) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (v) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and (E) each Z,independently of the others, is (i) a hydrogen atom, (ii) a halogenatom, (iii) a nitro group, (iv) an alkyl group, (v) an aryl group, (vi)an arylalkyl group, (vii) an alkylaryl group, (viii) a group of theformula

wherein R₇₀ is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, a silyl group, or a siloxy group, (ix) a sulfonyl groupof the formula —SO₂R₈₀ wherein R₈₀ is a hydrogen atom, an alkyl group,an aryl group, an arylalkyl group, an alkylaryl group, a silyl group, ora siloxy group, or (x) a phosphoryl group of the formula —PO₃R₉₀ whereinR₉₀ is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, a silyl group, or a siloxy group; saidmoieties being bonded to a central atom, monomeric group of atoms,oligomer, or polymer; (2) melting the ink; and (3) causing droplets ofthe melted ink to be ejected in an imagewise pattern onto a substrate.60. A process according to claim 59 wherein the printing apparatusemploys a piezoelectric printing process wherein droplets of the ink arecaused to be ejected in imagewise pattern by oscillations ofpiezoelectric vibrating elements.
 61. A process according to claim 59wherein the substrate is a final recording sheet and droplets of themelted ink are ejected in an imagewise pattern directly onto the finalrecording sheet.
 62. A process according to claim 59 wherein thesubstrate is an intermediate transfer member and droplets of the meltedink are ejected in an imagewise pattern onto the intermediate transfermember followed by transfer of the imagewise pattern from theintermediate transfer member to a final recording sheet.
 63. A processaccording to claim 62 wherein the intermediate transfer member is heatedto a temperature above that of the final recording sheet and below thatof the melted ink in the printing apparatus.